TW201022148A - Use of surfactant/defoamer mixtures for enhanced metals loading and surface passivation of silicon substrates - Google Patents

Use of surfactant/defoamer mixtures for enhanced metals loading and surface passivation of silicon substrates Download PDF

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TW201022148A
TW201022148A TW098133617A TW98133617A TW201022148A TW 201022148 A TW201022148 A TW 201022148A TW 098133617 A TW098133617 A TW 098133617A TW 98133617 A TW98133617 A TW 98133617A TW 201022148 A TW201022148 A TW 201022148A
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acid
removal composition
polymer
composition
microelectronic device
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TW098133617A
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TWI485110B (en
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Michael B Korzenski
Ping Jiang
Charles Beall
Mick Bjelopavlic
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Advanced Tech Materials
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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
    • H01L21/31—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26 to form insulating layers thereon, e.g. for masking or by using photolithographic techniques; After treatment of these layers; Selection of materials for these layers
    • H01L21/3105—After-treatment
    • H01L21/311—Etching the insulating layers by chemical or physical means
    • H01L21/31105—Etching inorganic layers
    • H01L21/31111—Etching inorganic layers by chemical means
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    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K13/00—Etching, surface-brightening or pickling compositions
    • C09K13/04—Etching, surface-brightening or pickling compositions containing an inorganic acid
    • C09K13/08—Etching, surface-brightening or pickling compositions containing an inorganic acid containing a fluorine compound
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    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
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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
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/008—Polymeric surface-active agents
    • 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
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/66—Non-ionic compounds
    • C11D1/72—Ethers of polyoxyalkylene glycols
    • 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
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/66—Non-ionic compounds
    • C11D1/78—Neutral esters of acids of phosphorus
    • 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
    • C11D3/0026—Low foaming or foam regulating 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
    • C11D3/042—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
    • C11D3/20—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
    • C11D3/37—Polymers
    • 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
    • C11D3/37—Polymers
    • C11D3/3703—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • C11D3/3707—Polyethers, e.g. polyalkyleneoxides
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
    • C23F1/00—Etching metallic material by chemical means
    • C23F1/10—Etching compositions
    • C23F1/14—Aqueous compositions
    • C23F1/16—Acidic compositions
    • C23F1/18—Acidic compositions for etching copper or alloys thereof
    • 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
    • H01L21/02002—Preparing wafers
    • H01L21/02005—Preparing bulk and homogeneous wafers
    • H01L21/02032—Preparing bulk and homogeneous wafers by reclaiming or re-processing
    • 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
    • H01L21/31—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26 to form insulating layers thereon, e.g. for masking or by using photolithographic techniques; After treatment of these layers; Selection of materials for these layers
    • H01L21/3205—Deposition of non-insulating-, e.g. conductive- or resistive-, layers on insulating layers; After-treatment of these layers
    • H01L21/321—After treatment
    • H01L21/3213—Physical or chemical etching of the layers, e.g. to produce a patterned layer from a pre-deposited extensive layer
    • H01L21/32133—Physical or chemical etching of the layers, e.g. to produce a patterned layer from a pre-deposited extensive layer by chemical means only
    • H01L21/32134—Physical or chemical etching of the layers, e.g. to produce a patterned layer from a pre-deposited extensive layer by chemical means only by liquid etching only
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    • 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
    • C11D2111/00—Cleaning compositions characterised by the objects to be cleaned; Cleaning compositions characterised by non-standard cleaning or washing processes
    • C11D2111/10—Objects to be cleaned
    • C11D2111/14—Hard surfaces
    • C11D2111/22—Electronic devices, e.g. PCBs or semiconductors

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Abstract

Removal compositions and processes for removing at least one material layer from a rejected microelectronic device structure having same thereon. The removal composition includes hydrofluoric acid. The composition achieves substantial removal of the material(s) to be removed while not damaging the layers to be retained, for reclaiming, reworking, recycling and/or reuse of said structure.

Description

201022148 六、發明說明： 【發明所屬之技術領域】 本發明概言之係關於將材料層（例如，低-k介電質）自其 上具有該材料之基板或物件移除以回收、再加工、再循環 利用及/或再使用該基板或物件之方法，且係關於使用其 '製造之產品。 【先前技術】 隨著裝置尺寸降低，對與高密度、超大規模積體（ULSI) 半導體佈線相關性能逐漸增加之需求曰益需要使用低介電 常數（低-k)絕緣層以增加信號傳輸速度。 典型低-k材料包括使用市售前體沈積之碳摻雜氧化物 (CDO)，例如 SiLK™、AURORA™、CORAL™、或黑金剛 石（BLACK DIAMOND)™，例如使用專有黑金剛石™方 法。該等CDO通常使用化學蒸氣沈積（CVD)方法自有機矽 烷及有機矽氧烷前體形成。CVD碳摻雜氧化物低-k介電質 通常由整體介電常數小於約3.2之多孔低密度材料構成， 且通常藉由在已形成之其他半導體結構（例如金屬互連線 及通孔）内形成多個CDO層來用於各種半導體結構中。舉 例而言，CD◦可用作介電絕緣層（金屬間介電（IMD)層）、 '覆蓋層及/或某些結構之間隙填充材料。 經常地，在多層裝置製造製程或鑒定製程期間在不可接 受的層處理之後，微電子裝置晶圓（例如矽半導體晶圓）必 須廢棄。可能出現許多處理問題，例如，層之不均勻沈積 或後續蝕刻誤差。在選定處理步驟之後實施許多品質控制 143740.doc 201022148 測試方法，由此可能使可接受的半導體晶圓因各種原因而 被拒絕並「廢棄」，此導致重大的非生產成本。除不合格 晶圓以外’測試晶圓通常由於不能回收或再循環利用某此 膜類型而被廢棄。測試晶圓支出在工廠的前三大材料費用 中。 現有技術實踐已將不合格或廢棄的製程晶圓送回至晶圓 供應商用以處理’藉此使用化學及機械方法自半導體晶圓 移除材料層（例如，介電層，例如CDO層）用以再使用該晶 圓。成功移除介電層及上覆於晶圓之其他特徵之後，使晶 圓在新的多層半導鱧裝置製造製程中再循環利用或再使 用。隨著半導體晶圓製造向較大直徑晶圓（例如丨2英吋晶 圓）之轉移，廢棄及再循環利用出廠製程晶圓由於高非生 產性成本而日益而變得越來越缺乏吸引力。 本文揭示經改良組合物及方法’藉此至少一種材料（例 如，金屬堆疊材料、蚀刻終止層 '光阻劑、障壁層、及/ 或包括高-k及低-k層在内的介電層）可自微電子裝置結構移 除以回收、再加工、再循環利用、及/或再使用該等結 構，由此使組合物及方法與現有製造方法及組份相容。下 伏裝置基板（例如，矽）較佳不會被該移除組合物損壞。較 佳地，使用該等組合物自微電子裝置移除材料（例如，低_k 介電質層）之方法可在單一步驟中實施，且因此不需要高 能耗的氧化步驟。 除移除材料層同時使對下伏基板材料之損壞降至最低以 外，本發明之組合物可經調配以符合當地環境要求。例 143740.doc 201022148 如，高氟化物濃度及高有機溶劑濃度可使得組合物由於廢 水處置問題而難以用於大量製造中。視調配物之化學需氧 量（COD)之值（其中溶液之COD係在強氧化劑之存在下在酸 性條件下可完全氧化成二氧化碳之有機化合物量之量度） 而定，可能不允許調配物存於設備廢水中而直接返回至環 境中。舉例而言，在瑞士（Switzerland) ’廢水樣品之COD 必須降至200與1000 mg/L之間廢水或工業水才能返回至環 境中（Pupunat，L.、Sollberger，F.、Rychen，P. ’ 「Efficient Reduction of Chemical Oxygen Demand in Industrial Wastewaters,」 http://www.csem.ch/corporate/Report2002/pdf/p56.pdf) 0 若廢水僅含有氟化物源（無有機溶劑），則可使用氟化物 處理系統來首先從廢水中移除氟化物，且然後可將水排放 至環境中。若廢水僅含有有機溶劑（無氟化物源），可使用 有機處置系統（例如焚化爐）。不利地是，焚化系統不能接 受含高氟化物濃度之廢水樣品，此乃因氟化物源可損壞焚 化爐構造材料。 因此，除提供用於自微電子裝置結構移除至少一種材料 用以回收、再加工、再循環利用、及/或再使用該等結構 之經改良組合物及方法以外，該組合物及/或使用該組合 物之方法較佳符合與該組合物之處置有關的當地規定標 準。 【發明内容】 本文揭示組合物及方法，其中該等組合物及方法用於將 至少一種材料（例如，介電及/或其他材料層）自其上具有該 143740.doc 201022148 材料之微電子裝置結構移除用以回收、再加工、再循環利 用、及/或再使用該微電子裝置結構，且揭示使用移除組 合物之方法及使用其製造之產品或中間產品。 在一個態樣中，揭示一種移除組合物，該移除組合物包 含至少一種蝕刻劑、至少一種界面活化劑/聚合物源視 情況至少一種有機溶劑、視情況至少一種螯合劑、視情況 至少一種氧化劑、視情況至少一種氣化物源、視情況至少 一種消泡劑、及視情況水。 在另一態樣中，揭示一種移除組合物，該移除組合物包 含至少一種蝕刻劑、至少一種界面活化劑/聚合物源、水 及視情況至少一種消泡劑。 在又一態樣中，揭示一種移除組合物，該移除組合物包 含至少一種钱刻舞！、至少一種界面活化劑/聚合物源、水 及至少-種消泡劑’其中該消泡劑包含選自由以下組成之 群之物質：冑氧乙烧/環氧丙垸喪段共聚#、醇烧氧基化 物月曰肪烧氧基化#、碟酸醋與非離子乳化劑之推合 物、及其組合。 在再嘘樣中，揭示再循環利用微電子裝置結構之方 法該方法包含.使微電子裝置結構與移除組合物在足以 實質上自該微電子裝置結構移除至少—種材料之條件下接 觸足夠時間以獲得可再循環利用或可再使用之微電子震置 基板該微電子I置結構包含微電子裝置基板及至少—種 =自由以下組成之群之可移除材料：#刻後殘餘物、低_k ”電質呵-k介電質、蝕刻終止材料、金屬堆疊材料、障 J43740.doc 201022148 壁層材料、鐵電材料、石夕化物材料、氮化物材料、氧化物 材料、光㈣、底部抗反射塗層（BARC)、犧牲性抗反射 塗層（SARC)、含聚合物之累積物、其他材料、經換雜區 - 其、及σ，其中該移除組合物包含至少一種银刻劑、 至少一種界面活化劑/聚合物源、視情況至少一種有機溶 劑、視情況至少-種整合劑、視情況至少一種氧化劑、視 情況至少一種氣化物源、視情況至少一種消泡劑、及視情 況水。在較佳實施例中，該移除組合物包含至少一種消泡 劑，其中該消泡劑包含選自由以下組成之群之物質：環氧 乙院/環氧丙垸嵌段共聚物、醇院氧基化物、脂肪醇烧氧 基化物、磷酸酯與非離子乳化劑之摻合物、及其組合。 在再一態樣中，揭示一種套組，該套組在一或多個容器 或夕種用於形成移除組合物之以下試劑，其中該 移除組合物包含至少一種蝕刻劑、至少一種界面活化劑: 聚合物源、視情況至少一種有機溶劑、視情況至少一種螯 合劑、視情況至少一種氧化劑、視情況至少一種氣化物 源、視情況至少一種消泡劑、及視情況水，其中該套組適 於形成適用於將至少一種可移除材料自其上具有該材料之 微電子裝置結構移除的移除組合物，該可移除材料選自由 以下組成之群：蝕刻後殘餘物、低-k介電質、高_k介電 質、钱刻終止材料、金屬堆墨材料、障壁層材料、鐵電材 料、石夕化物材料、氮化物材料、氧化物材料、光阻劑、底 部抗反射塗層（BARC)、犧牲性抗反射塗層（SARC)、含聚 合物之累積物、其他材料、經摻雜區域、及其組合。 143740.doc 201022148 根據隨後之揭示内容及隨附申請專利範圍可更全面地瞭 解本發明之其他態樣、特徵及實施例。 【實施方式】 本發明概言之係關於移除組合物及方法，該等組合物及 方法用於將至少一個材料層（例如，介電材料（高k及/或 低-k)、金屬堆疊材料、蝕刻終止層、障壁層材料、矽化 物、鐵電材料、光阻劑、抗反射塗層、蝕刻後殘餘物等） 自其上具有該材料之微電子裝置結構移除用於回收再加 工、再循環利用及/或再使用該微電子裝置結構。該回 收、再加工、再循環利用、及/或再使用可在廠外或廠内 實施。 「微電子裝置」對應於經製造用於微電子、積體電路或 電腦晶片應用中之半導體基板、平板顯示器、相變記憶裝 置、太陽能面板及包括太陽能基板之其他產品、光電伏 打、及微機電系統（MEMS)。應理解，術語「微電子裝 置」、「微電子基板」及「微電子裝置結構」並非意欲以 任何方式加以限制且包括最終將成為微電子裝置或微電子 總成之任何基板或結構。微電子裝置可為圖案化毯覆之對 照及/或測試裝置。「不合格微電子裝置」結構意欲描述 根據本發明之方法可回收、再加工及/或清潔之所有微電 子裝置。 該「微電子$置結構」包括其上具有至少一種材料之 微電子裝置基板」’其中該至少一種材料組成上或晶體 明顯地不同於該微電子裝置基板。如本文所定義，「微電 143740.doc 201022148 子裝置基板」對應於任何基板，其包括（但不限於广裸 矽；多晶矽；鍺；m/v化合物，例如氮化鋁、氮化鎵砷 化鎵、磷化銦；鈦鐵礦；II/IV化合物；π/νι化合物，例如 CdSe、CdS、ZnS、ZnSe及CdTe ;碳化矽；藍寶石；藍寶 石上矽；碳；經摻雜玻璃；未經摻雜的玻璃；金剛石； GeAsSe玻璃；多晶矽（經摻雜或未經摻雜）；單晶矽（經摻 雜或未經摻雜广非晶矽、二硒化銅銦（鎵）；及其組合： 「材料」或「材料層」可包括（但不限於）至少一種選自由 以下組成之群之物質：經摻雜之磊晶矽、未經摻雜之磊晶 矽、蝕刻後殘餘物、低_k介電質、高吨介電質、蝕刻終止 材料、金屬堆疊材料、障壁層材料、鐵電材料、矽化物、 氮化物、氧化物、光阻劑、底部抗反射塗層（barc)、犧 牲性抗反射塗層（SARC)、含聚合物之累積物、其他材料、 經摻雜區域、及其組合。該等材料層中之至少一者可經至 少一種離子植入離子（例如硼、磷及砷）摻雜。如本文所定 義，「其他材料」包括含鉬的材料、含鑭的材料、含铑的 材料、含錳的材料（例如Μη〇χ)、碳奈米管、SrTi〇3、 Zr02、YV〇4、LiNb03、Te03、及其組合 β 本文所用「約」意欲對應於所述值±5〇/〇。 如本文所又義，「低_k介電材料」對應於在分層微電子 裝置中用作介電材料之任何材料，其中該材料具有小於約 4_〇之介電常數》較佳地，低_k介電材料包括低極性材料， 例如氧化矽、含矽之有機聚合物、含矽之混合有機/無機 材料、有機矽酸鹽玻璃（OSG)、TE〇s、氟化矽酸鹽玻璃 143740.doc -9- 201022148 (FSG)、SiCOH、及碳摻雜之氧化物（CDO)玻璃。應瞭解， 低-k介電材料可具有各種密度及各種多孔性。 如本文所定義，「金屬堆叠材料」及「金屬」對應於微 電子裝置上之组、氮化组、氮化钦、鈦、銻、銘、鎢、氮 化鎢、及上述金屬之矽化物；含銅層；含鋁層；Al/Cu 層；A1合金；Cu合金；含鈷層，例如CoWP及CoWBP ;含 金層；Au/Pt層；氧化铪；氧矽酸铪；氧化锆；氧化鑭； 鈦酸鹽；其氮摻雜之類似物；釕；銥；鎘；鉛；硒；銀； MoTa ;及其組合與鹽。 如本文所定義，「高-k介電」材料對應於：氧化铪（例 如，Hf02);氧化锆（例如，Zr02);氧矽酸铪；矽酸铪； 矽酸锆；矽酸鈦；氧化鋁；其鑭摻雜之類似物（例如， LaA103);矽酸鋁；鈦酸鹽（例如，Ta205);铪與矽之氧化 物及氮化物（例如，HfSiON);其鑭摻雜之類似物（例如， HFSiON(La));鈦酸鋇锶（BST);铪與鋁之氧化物（例如， HfxAlyOz);鈦酸锶（SrTi03);鈦酸鋇（BaTi03);及其組 合。 如本文所定義，「障壁層材料」對應於此項技術中用以 密封金屬線（例如，銅互連）以將該金屬（例如，銅）至介電 材料之擴散降至最低之任何材料。較佳障壁層材料包括富 石夕氮化物、富石夕氧氮化物、组、鈦、釕、給、鶴、及其他 難熔金屬及其氮化物與矽化物。 如本文所定義，「鐵電材料」包括（但不限於）：鈦酸鋇 (BaTi03);鈦酸鉛（PbTi03);锆鈦酸鉛（PZT);锆鈦酸鉛鑭 143740.doc -10- 201022148 (PLZT)；鈮酸鉛錳（PMN);鈮酸鉀（KNb03);鈮酸鉀鈉 (KxNaKxNb03);鈕鈮酸鉀（KCTaxNUOs);鈮酸鉛 (PbNb206);鈦酸鉍（Bi4Ti3012);鈮酸鉛鉍（PbBi2Nb209); 鈮酸鋰（LiNb〇3);鈕酸鋰（LiTa03);鈕酸锶鉍；鈮酸鳃 鉍；鈕酸鋰；鈦酸鳃；及其組合與鹽。 如本文所定義，「蝕刻終止層」包括碳化矽（SiC)、氮 化矽碳（SiCN)、氧化矽碳（SiCO)、氧氮化矽（SiON)、銅、 矽鍺（SiGe)、SiGeB、SiGeC、A1A、InGaP、InP、 InGaA、及其組合與鹽。 如本文所定義，「氧化物」包括在該等其他層中所定義 之任何氧化物化合物以及壓電材料（例如 (卩1)’81〇(21*，1^)03)、熱電材料（例如（？1)，€&)(21*，1^)03)、超導 體（例如YBCO)、電極（例如氧化銦錫）、熱障壁材料（例如201022148 VI. Description of the Invention: [Technical Field] The present invention relates to removing a material layer (for example, a low-k dielectric) from a substrate or an object having the material thereon for recycling and reprocessing A method of recycling and/or reusing the substrate or article, and relating to the use of the 'manufactured product. [Prior Art] As device size decreases, the need for increased performance associated with high density, ultra large scale integrated (ULSI) semiconductor wiring requires the use of low dielectric constant (low-k) insulating layers to increase signal transmission speed. . Typical low-k materials include carbon doped oxide (CDO) deposited using commercially available precursors, such as SiLKTM, AURORTM, CORALTM, or BLACK DIAMONDTM, for example using the proprietary Black DiamondTM method. These CDOs are typically formed from organodecane and organooxane precursors using chemical vapor deposition (CVD) processes. CVD carbon doped oxide low-k dielectrics are typically composed of porous low density materials having an overall dielectric constant of less than about 3.2, and are typically formed by other semiconductor structures (e.g., metal interconnects and vias) that have been formed. A plurality of CDO layers are formed for use in various semiconductor structures. For example, CD◦ can be used as a dielectric insulating layer (inter-metal dielectric (IMD) layer), a 'overlay layer, and/or some structure of gap fill material. Frequently, microelectronic device wafers (e.g., germanium semiconductor wafers) must be discarded after unacceptable layer processing during the multilayer device fabrication process or qualification process. Many processing issues may arise, such as uneven deposition of layers or subsequent etching errors. Many quality control 143740.doc 201022148 test methods are implemented after the selected processing steps, which may result in acceptable semiconductor wafers being rejected and "discarded" for various reasons, which results in significant non-production costs. In addition to failed wafers, test wafers are typically discarded due to the inability to recycle or recycle certain membrane types. Test wafer expenses are among the top three material costs of the plant. Prior art practices have returned unqualified or discarded process wafers to a wafer supplier for processing 'by thereby removing chemical material from a semiconductor wafer (eg, a dielectric layer, such as a CDO layer) using chemical and mechanical methods. To reuse the wafer. After successful removal of the dielectric layer and other features overlying the wafer, the wafer is recycled or reused in a new multilayer semi-conducting device fabrication process. As semiconductor wafer fabrication moves to larger diameter wafers (eg, 2 inch wafers), waste and recycling of factory-processed wafers is increasingly becoming less attractive due to high non-productive costs. . The improved compositions and methods are disclosed herein by means of at least one material (eg, metal stack material, etch stop layer photoresist, barrier layer, and/or dielectric layer including high-k and low-k layers) The structure can be removed from the microelectronic device for recycling, reprocessing, recycling, and/or reuse, thereby rendering the composition and method compatible with existing manufacturing methods and components. The underlying device substrate (e.g., crucible) is preferably not damaged by the removal composition. Preferably, the method of removing materials (e.g., low-k dielectric layers) from the microelectronic device using such compositions can be carried out in a single step, and thus does not require a high energy oxidative step. In addition to removing the layer of material while minimizing damage to the underlying substrate material, the compositions of the present invention can be formulated to meet local environmental requirements. Example 143740.doc 201022148 For example, high fluoride concentrations and high organic solvent concentrations can make the composition difficult to use in mass production due to waste water disposal issues. Depending on the chemical oxygen demand (COD) of the formulation (where the COD of the solution is a measure of the amount of organic compound that can be completely oxidized to carbon dioxide under acidic conditions in the presence of a strong oxidant), the formulation may not be allowed to accumulate Return directly to the environment in the wastewater of the equipment. For example, in Switzerland (Switzerland) the COD of wastewater samples must be reduced to between 200 and 1000 mg/L of wastewater or industrial water to return to the environment (Pupunat, L., Sollberger, F., Rychen, P. ' "Efficient Reduction of Chemical Oxygen Demand in Industrial Wastewaters," http://www.csem.ch/corporate/Report2002/pdf/p56.pdf) 0 If the wastewater contains only a fluoride source (no organic solvent), then fluorine can be used. The treatment system first removes fluoride from the wastewater and can then discharge the water into the environment. If the wastewater contains only organic solvents (no fluoride source), an organic disposal system (such as an incinerator) can be used. Disadvantageously, the incineration system cannot accept wastewater samples containing high fluoride concentrations because the fluoride source can damage the incinerator construction materials. Thus, in addition to providing improved compositions and methods for removing, reprocessing, recycling, and/or reusing at least one material from a microelectronic device structure, the composition and/or The method of using the composition preferably conforms to local regulatory standards associated with the disposal of the composition. SUMMARY OF THE INVENTION Disclosed herein are compositions and methods for using at least one material (eg, a layer of dielectric and/or other materials) from a microelectronic device having the 143740.doc 201022148 material thereon The structure is removed for recycling, reprocessing, recycling, and/or reuse of the microelectronic device structure, and discloses methods of using the removed composition and products or intermediate products made therefrom. In one aspect, a removal composition is disclosed, the removal composition comprising at least one etchant, at least one interfacial activator/polymer source, optionally at least one organic solvent, optionally at least one chelating agent, optionally at least An oxidizing agent, optionally at least one vapor source, optionally at least one antifoaming agent, and optionally water. In another aspect, a removal composition is disclosed, the removal composition comprising at least one etchant, at least one interface activator/polymer source, water, and optionally at least one antifoaming agent. In yet another aspect, a removal composition is disclosed that includes at least one money to dance! , at least one interface activator/polymer source, water, and at least one antifoaming agent, wherein the antifoaming agent comprises a substance selected from the group consisting of: oxime/ep-propyl oxime copolymerization #, alcohol An alkoxylate sulphate oxyalkylation #, a fermented vinegar and a nonionic emulsifier, and combinations thereof. In a further example, a method of recycling a microelectronic device structure is disclosed, the method comprising: contacting a microelectronic device structure and a removal composition under conditions sufficient to substantially remove at least one material from the microelectronic device structure Sufficient time to obtain a recyclable or reusable microelectronic substrate. The microelectronic I structure comprises a microelectronic device substrate and at least one type of free material of the following composition: #刻后遗物, low _k ” electric quality κ-k dielectric, etch stop material, metal stack material, barrier J43740.doc 201022148 wall material, ferroelectric material, lithium material, nitride material, oxide material, light (4) a bottom anti-reflective coating (BARC), a sacrificial anti-reflective coating (SARC), a polymer-containing buildup, other materials, a modified zone - and σ thereof, wherein the removal composition comprises at least one silver An engraving agent, at least one interfacial activator/polymer source, optionally at least one organic solvent, optionally at least one integrator, optionally at least one oxidizing agent, optionally at least one vapor source, In the case of at least one antifoaming agent, and optionally water. In a preferred embodiment, the removal composition comprises at least one antifoaming agent, wherein the antifoaming agent comprises a material selected from the group consisting of: Epoxy /epoxypropene block copolymer, alcoholic anhydride, fatty alcohol alkoxylate, blend of phosphate and nonionic emulsifier, and combinations thereof. In still another aspect, a kit is disclosed The kit is used to form a reagent for removing the composition in one or more containers or in the evening, wherein the removal composition comprises at least one etchant, at least one interfacial activator: a polymer source, optionally at least one An organic solvent, optionally at least one chelating agent, optionally at least one oxidizing agent, optionally at least one vapor source, optionally at least one antifoaming agent, and optionally water, wherein the kit is adapted to form at least one suitable Removing the removal composition of the material from the structure of the microelectronic device having the material thereon, the removable material being selected from the group consisting of: post-etch residues, low-k dielectric, high-k dielectric Electricity , money engraving material, metal stacking material, barrier layer material, ferroelectric material, lithium material, nitride material, oxide material, photoresist, bottom anti-reflective coating (BARC), sacrificial anti-reflective coating Layer (SARC), polymer-containing buildup, other materials, doped regions, and combinations thereof. 143740.doc 201022148 A more complete understanding of other aspects of the present invention can be obtained from the following disclosure and the accompanying claims. BRIEF DESCRIPTION OF THE DRAWINGS [Invention] The present invention relates generally to a removal composition and method for using at least one material layer (eg, a dielectric material (high k and/or low) -k), metal stack material, etch stop layer, barrier layer material, germanide, ferroelectric material, photoresist, anti-reflective coating, post-etch residue, etc.) from the structure of the microelectronic device having the material thereon In addition to being used for recycling, recycling, and/or reusing the microelectronic device structure. This recycling, reprocessing, recycling, and/or reuse can be performed off-site or in-plant. "Microelectronics devices" correspond to semiconductor substrates, flat panel displays, phase change memory devices, solar panels, and other products including solar substrates, which are manufactured for use in microelectronics, integrated circuits or computer chip applications, photovoltaics, and micro Electromechanical systems (MEMS). It should be understood that the terms "microelectronic device", "microelectronic substrate" and "microelectronic device structure" are not intended to be limiting in any way and include any substrate or structure that will ultimately become a microelectronic device or microelectronic assembly. The microelectronic device can be a patterned blanket overlay and/or test device. The "failed microelectronic device" structure is intended to describe all of the microelectronic devices that can be recycled, reprocessed, and/or cleaned in accordance with the methods of the present invention. The "microelectronics" structure includes a microelectronic device substrate having at least one material thereon" wherein the at least one material composition or crystal is significantly different from the microelectronic device substrate. As defined herein, "Micro-Electronic 143740.doc 201022148 Sub-Device Substrate" corresponds to any substrate including, but not limited to, wide bare 矽; polycrystalline germanium; germanium; m/v compounds such as aluminum nitride, gallium arsenide arsenide Gallium, indium phosphide; ilmenite; II/IV compound; π/νι compound, such as CdSe, CdS, ZnS, ZnSe and CdTe; tantalum carbide; sapphire; sapphire; carbon; doped glass; Miscellaneous glass; diamond; GeAsSe glass; polycrystalline germanium (doped or undoped); single crystal germanium (doped or undoped wide amorphous germanium, copper indium diselenide (gallium); and combinations thereof "Material" or "material layer" may include, but is not limited to, at least one selected from the group consisting of: doped epitaxial germanium, undoped epitaxial germanium, post-etch residue, low _k dielectric, high-ton dielectric, etch stop material, metal stack material, barrier layer material, ferroelectric material, germanide, nitride, oxide, photoresist, bottom anti-reflective coating (barc), Sacrificial anti-reflective coating (SARC), polymer-containing buildup, a material, a doped region, and combinations thereof. At least one of the layers of the material may be doped with at least one ion implanted ion (eg, boron, phosphorus, and arsenic). As defined herein, "other materials" include Molybdenum materials, niobium-containing materials, niobium-containing materials, manganese-containing materials (eg, Μη〇χ), carbon nanotubes, SrTi〇3, Zr02, YV〇4, LiNb03, Te03, and combinations thereof "约约" is intended to correspond to the stated value ± 5 〇 / 〇. As used herein, "low _k dielectric material" corresponds to any material used as a dielectric material in a layered microelectronic device, wherein the material Preferably, the low-k dielectric material comprises a low polarity material such as cerium oxide, cerium-containing organic polymer, cerium-containing mixed organic/inorganic material, organic cerium salt Glass (OSG), TE〇s, fluorite silicate glass 143740.doc -9- 201022148 (FSG), SiCOH, and carbon doped oxide (CDO) glass. It should be understood that low-k dielectric materials can be Has a variety of densities and various porosity. As defined herein, "metal stacking materials" and " Corresponding to the group on the microelectronic device, the nitrided group, the nitrided, titanium, tantalum, tungsten, tungsten nitride, and the metal halide; the copper layer; the aluminum layer; the Al/Cu layer A1 alloy; Cu alloy; cobalt-containing layer, such as CoWP and CoWBP; gold-containing layer; Au/Pt layer; ruthenium oxide; bismuth oxyhydroxide; zirconia; ruthenium oxide; titanate; ; 钌; 铱; cadmium; lead; selenium; silver; MoTa; and combinations thereof and salts. As defined herein, "high-k dielectric" material corresponds to: yttrium oxide (eg, Hf02); zirconia (eg, ZrO2); bismuth oxyhydroxide; bismuth ruthenate; zirconium ruthenate; titanium ruthenate; aluminum oxide; bismuth doped analog (for example, LaA103); aluminum citrate; titanate (for example, Ta205); An oxide and a nitride (for example, HfSiON); an antimony doped analog (for example, HFSiON (La)); barium titanate (BST); an oxide of barium and aluminum (for example, HfxAlyOz); Barium titanate (SrTi03); barium titanate (BaTi03); and combinations thereof. As defined herein, "barrier layer material" corresponds to any material used in the art to seal metal lines (e.g., copper interconnects) to minimize diffusion of the metal (e.g., copper) to dielectric materials. Preferred barrier layer materials include Fu Shi Xi nitride, Fu Shi Xi oxynitride, group, titanium, tantalum, niobium, crane, and other refractory metals and their nitrides and tellurides. As defined herein, "ferroelectric materials" include, but are not limited to, barium titanate (BaTi03); lead titanate (PbTi03); lead zirconate titanate (PZT); lead zirconate titanate 143740.doc -10- 201022148 (PLZT); lead manganese citrate (PMN); potassium citrate (KNb03); sodium potassium citrate (KxNaKxNb03); potassium citrate (KCTaxNUOs); lead citrate (PbNb206); barium titanate (Bi4Ti3012); Lead bismuth citrate (PbBi2Nb209); lithium niobate (LiNb〇3); lithium nitrite (LiTa03); bismuth citrate; bismuth citrate; lithium nitrite; barium titanate; and combinations and salts thereof. As defined herein, an "etch stop layer" includes tantalum carbide (SiC), tantalum nitride (SiCN), tantalum carbon (SiCO), tantalum oxynitride (SiON), copper, germanium (SiGe), SiGeB, SiGeC, A1A, InGaP, InP, InGaA, and combinations thereof and salts. As defined herein, "oxide" includes any oxide compound as defined in such other layers as well as piezoelectric materials (eg, (卩1) '81〇(21*,1^)03), thermoelectric materials (eg, (?1), €&) (21*, 1^) 03), superconductor (eg YBCO), electrode (eg indium tin oxide), thermal barrier material (eg

Zr02、Ce02、Y2〇3、Mg〇、Al2〇3、及 Si02)、光學塗層（例 如 Ti02、Ta205、Y2〇3、及 Sc2〇3)、及導電膜（例如 La(i X)Zr02, Ce02, Y2〇3, Mg〇, Al2〇3, and SiO2), optical coatings (such as Ti02, Ta205, Y2〇3, and Sc2〇3), and conductive films (such as La(i X)

SrxGa(1_y)My03(其中 M=Fe、Co、Ni)、La(1.x)SrxMn03、及SrxGa(1_y)My03 (where M=Fe, Co, Ni), La(1.x)SrxMn03, and

La(i-x)CaxMn〇3) 〇 如本文所定義，「含聚合物之累積物」對應於在製造期 間累積於微電子裝置基板之背側及斜邊緣上之材料且包括 沈積於微電子裝置該點之任何材料，其包括（但不限於）低-k介電質、高-k介電質、蝕刻終止材料、金屬堆疊材料、 障壁層材料、鐵電材料、矽化物、氮化物、氧化物、光阻 劑、底部抗反射塗層（BARC)、犧牲性抗反射塗層 (SARC)、其他材料、摻雜劑、及其組合。 143740.doc 201022148 如本文所用，「回收」微電子裝置結構對應於實質上移 除至少一種毗鄰欲保留層之材料而不會實質上損壞該（等） 欲保留層，其中欲移除之該（等）材料包括（但不限於）蝕刻 後殘餘物、㈣終止層、金屬堆叠材料、障壁層材料、鐵 電材料、％化物、氮化物 '氡化物、介電質（低_k及/或高_ k)、含聚合物之累積物、經摻雜區域(不包括經摻雜之磊晶 層）、及其組合。欲保留之該（等）層選自由微電子裝置基 板、經摻雜之蟲晶石夕、未經摻雜之蟲晶石夕、钱刻終止層、 金屬堆疊材料、障壁層材料、鐵電材料、矽化物、氮化 物、介電質（低-k及/或高_k)、經摻雜區域、及其組合組成 之群。回收可在薇外或在廢内實施。應瞭解欲移除之材 料與欲保留之層不能為同-物質。舉例而言，欲移除之材 料可包括低-k介電材料且欲保留之層可為微電子裝置基 板。熟悉此項技術者應瞭解，使用本揭示内容可確定可^ 用何種組合物及方法以在保留特定層㈣時移除特定材 料。 如本文所疋義實質上移除（substantial rem〇val或 ⑽—卜咖㈣」對應於移除至少90 wt.%的期望移 除之材料、更佳地至少95 wt%、甚至更佳地至少” 败％、甚至更佳地至少98wt.%、且最佳至少的心。 如本文所用#加工」微電子裝置結構對應於在微影 顯影且未通過品質控制測試之後實質上移除光阻了 抗反射塗層（ARC)、含聚人鉍+ w ± 眾口物之累積物、蝕刻後殘餘物、 電鑛銅、及其組合中之至少一者。或者，再加工包括移除 143740.doc •12- 201022148 微電子裝置結構之背側及/或斜邊緣上之含聚合物之累積 物。再加工可在廠外或在廠内實施。再加工之後，微電子 裝置結構可重新塗佈、烘烤並根據此項技術中習知之光微 影技術重新圖案化。 如本文所定義，「再循環利用」定義為在如本文所述移 除材料之後回收並重新使用或再加工並重新使用微電子裝 置之保留層。舉例而言，再循環利用微電子裝置可重新引 入製造處理流令’可用作對照或測試裝置，或可用於非相 關製程或非相關產品中。 如本文所定義，「實質上消除」坑蝕係指與使用此項 技術已知之移除級合物通常所觀察到之坑蝕相比坑蝕減 少。較佳地’坑蝕之程度小於使用其他移除組合物所觀察 到坑蝕的10%、更佳地小於5%、且最佳小於2%。 應理解’欲回收之微電子裝置結構包括選自由以下組成 之群之基板：裸矽；多晶矽；鍺；In/V化合物，例如氮化 鎵、砷化鎵、磷化銦；鈦鐵礦；II/IV化合物；II/VI化合 物’例如CdSe、CdS、ZnS、ZnSe及CdTe ;碳化矽；藍寶 石，藍寶石上矽；碳；經摻雜玻璃；未經摻雜的玻璃；金 剛石；GeAsSe玻璃；及其組合，且可為此項技術中習用之 任何直徑或厚度。舉例而言，此項技術中習用之基板直徑 包括200 mm、300 mm、4英吋、6英吋、且在未來450 mm。300 mm基板之厚度為750 μιη，與300 mm基板相比， 其他基板之厚度與直徑成正比。 成功回收之要求包括（但不限於）零或可忽略的前側、斜 143740.doc -13- 201022148 邊緣、及/或背侧石夕坑钱；0.2 5 pm的粒子少於25個，〇 12 μηι的粒子少於50個或0.09 μπι的粒子少於100個，總厚度變 化（TTV)小於約5 μπι ’表面金屬污染小於1χ1〇1〇個原子 cm·2 ;及/或所回收基板之厚度（無任何其他保留層）在初始 基板厚度的5%以内，較佳在2%以内，且最佳在1 %以内。 如本文所定義，「總厚度變化」對應於微電子裝置晶圓之 最大厚度與最小厚度間之絕對差異，如使用此項技術中習 知之厚度掃描或一系列點厚度量測所確定。 成功晶圓再加工之要求包括（但不限於）將光阻劑、含聚 合物之累積物、及/或電鍍銅自裝置基板之最外邊緣及背 侧實質上移除而不會實質上損壞欲保留之層，此在後續處 理期間減少粒子及金屬污染。 移除組合物可體現為眾多種特定調配物，如下文中更全 面地闞述。 在所有該等組合物中’組合物之特定組份皆參照包括零 下限在内之重量百分比範圍來論述，因而應理解，在組合 物之各特定實施例中可存在或不存在該等組份，且在存在 該等組份之情況下，以使用該等組份之組合物之總重量 計，該等組份可以低至〇 〇〇1重量％之濃度存在。 在一個態樣中，闞述符合國内及國際環境標準之移除組 合物（所謂的」綠色」移除組合物）。二乙二醇丁醚及其他 含伸乙基之溶劑係HAP化學品且可危害環境。舉例而言， 二乙二醇丁醚具有極高的化學需氧量（COD)值，該值係每 升/合液所消耗氧的質量。由於二乙二醇丁醚之高值， 143740.doc • 14- 201022148 在各個國家其已經被禁止或限制至極低含量。 第一態樣之「綠色」或「環境友好」移除組合物可包括 蝕刻劑源、至少一種界面活化劑、視情況水、視情況至少 一種有機溶劑、視情況至少一種有機酸、視情況至少一種 氧化劑、視情況至少一種氯化物源、視情況至少一種螯合 劑、及視情況至少一種消泡劑，該等基於組合物之總重量 以以下範圍存在： 組份 重量％ 钱刻劑 約0.01%至約90% 界面活化劑 約0.01 %至約15% 可選有機溶劑 0至約25% 可選有機酸 0至約25% 可選螯合劑 0至約25% 可選氧化劑 0至約25% 可選氣化物源 0至約25% 可選消泡劑 0至約5% 水 0至約99% 第一態樣之「綠色」移除組合物可包含至少一種蝕刻 劑、至少一種界面活化劑、視情況水、視情況至少一種有 機溶劑、視情況至少一種有機酸、視情況至少一種氧化 劑、視情況至少一種氣化物源、視情況至少一種螯合劑、 及視情況至少一種消泡劑，由該等構成或基本上由該等構 成。通常，蝕刻劑源、界面活化劑、可選水、可選有機溶 劑、可選有機酸、可選氧化劑、視情況氯化物源、可選螯 合劑、及可選消泡劑相對於彼此之特定比例及量可適當改 變以對選自由以下組成之群之材料提供合意的組合物移除 作用：姓刻後殘餘物、低-k介電材料、高-k介電材料、障 143740.doc -15- 201022148 壁層材料、鐵電材料、氮化物、矽化物、氧化物、含聚合 物之累積物、ARC材料、經摻雜區域、其他材料、及其組 合；及/或處理設備，如熟悉此項技術者無需過多努力即 可容易地確定者。在較佳實施例中，第一態樣之「綠色」 移除組合物實質上沒有胺。本文所定義，「實質上沒有」 對應於以該組合物之總重量計小於組合物之約1 wt %、更 佳小於0.5 wt·%、且最佳小於〇1 wt.%。 當用去離子水20:1稀釋時，第一態樣之「綠色」移除組 合物的pH值在約〇至約7、更佳地約2 · 5至約4.5、最佳約3 至約3.5之範圍内。 蝕刻劑可包括（但不限於）氟化物、胺及/或氫氡化物鹽’ 其包括以下至少一種：氟化氫（HF);二氟化氙（XeF2);氟 化鍵（NHJ);四烷基氟化銨（nrj);烷基氟化氫 (NRHJ);二氟化氫銨（nha);二烷基氟化氫銨 (ΝΙΗβ);三烷基氟化氫銨（nihf);三烷基三氟化氫銨 (NR_3:3HF)，無水氟化氫D比咬錯合物；無水氟化氫三乙胺 錯合物’胺氟化氫錯合物’其中r可彼此相同或不同且選 自由直鏈或具支鏈Ci-C6烷基組成之群（例如，甲基、乙 基、丙基、丁基、戊基、己基），且其中該胺包括直鏈或 具支鏈Ci-Cso烷基胺、經取代或未經取代芳基 胺、乙二醇胺、烷醇胺及胺_N_氧化物，其包括（但不限 於）：吡啶；2-乙基吡啶；2-曱氧基吡啶及其衍生物，例如 3-甲氧基0比咬，2-甲基<»比D定；〇比咬衍生物；二甲基〇比咬； 六氫》比啶；哌嗪；三乙胺；三乙醇胺；乙胺、甲胺、異丁 143740.doc -16 · 201022148 胺、第三丁基胺、三丁胺、二丙胺、二曱胺、二乙二醇 胺，早乙醇胺；"比嘻；異》惡唾；1，2,4-三唾；聯η比咬；喷 咬；°比嗪；建唤；啥琳；異喧琳；吲嗓；喷唾；Ν-甲基嗎 啉-Ν-氧化物（NMMO);三曱胺-Ν-氧化物；三乙胺氺氧化 物；°比啶-Ν-氧化物；Ν-乙基嗎啉-Ν-氧化物；Ν-曱基吡嘻 咬-Ν-氧化物；Ν-乙基'•比洛咬-Ν-氧化物；1-甲基咪吐；二 異丙胺；二異丁胺；苯胺；苯胺衍生物；及其組合。或 者’姓刻劑可包含氫氧化物鹽，其包括（但不限於）鹼金屬 氫氧化物、驗土金屬氫氧化物、四級胺氫氧化物、及其組 合。較佳地’蝕刻劑包含氟化氫。 所預期之界面活化劑包括陰離子、陽離子（基於四級銨 陽離子）及/或兩性離子界面活化劑。舉例而言，適宜非離 子界面活化劑可包括氟烷基界面活化劑、乙氧基化氟界面 活化劑、聚乙二醇、聚丙二醇、聚乙二醇醚或聚丙二醇 喊、綾酸鹽、十二烷基苯磺酸或其鹽、聚丙烯酸酯聚合 物、二壬基苯基聚氧乙烯、聚矽氧或經改良聚矽氧聚合 物、乙快系二醇或經改良乙炔系二醇、烷基銨或經改良烷 基銨鹽、及烷基酚聚縮水甘油醚、以及包含上述至少一種 之組合。在較佳實施例中，非離子界面活化劑可為乙氧基 化氟界面活化劑，例如ZONYL® FSO-lOO氟界面活化劑 (DuPont Canada公司 ’ Mississauga, Ontario，Canada)。本 發明組合物中預期之陰離子界面活化劑包括（但不限於）氟 界面活化劑’例如z〇NYl® UR 及 ZONYL® FS-62(DuPontLa(ix)CaxMn〇3) As defined herein, "polymer-containing buildup" corresponds to materials accumulated on the backside and beveled edges of the microelectronic device substrate during fabrication and includes deposition on a microelectronic device. Any material of the point including, but not limited to, low-k dielectric, high-k dielectric, etch stop material, metal stack material, barrier layer material, ferroelectric material, germanide, nitride, oxide , photoresist, bottom anti-reflective coating (BARC), sacrificial anti-reflective coating (SARC), other materials, dopants, and combinations thereof. 143740.doc 201022148 As used herein, "recycling" a microelectronic device structure corresponds to substantially removing at least one material adjacent to the layer to be retained without substantially damaging the layer to be retained, wherein the layer to be removed is Materials include, but are not limited to, post-etch residues, (iv) termination layers, metal stack materials, barrier layer materials, ferroelectric materials, % compounds, nitrides, germanium, dielectrics (low_k and/or high) _ k), polymer-containing buildup, doped regions (excluding doped epitaxial layers), and combinations thereof. The (etc.) layer to be retained is selected from the group consisting of a microelectronic device substrate, a doped smectite, an undoped smectite, a carbon stop layer, a metal stack material, a barrier layer material, a ferroelectric material. a group consisting of a telluride, a nitride, a dielectric (low-k and/or high-k), a doped region, and combinations thereof. Recycling can be carried out outside of Wei or in waste. It should be understood that the material to be removed cannot be the same substance as the layer to be retained. For example, the material to be removed may comprise a low-k dielectric material and the layer to be retained may be a microelectronic device substrate. Those skilled in the art will appreciate that the present disclosure can be used to determine which compositions and methods are available to remove a particular material while retaining a particular layer (4). Substantially removing (substantial rem〇val or (10) - 卜 (4)" as used herein corresponds to removing at least 90 wt.% of the material desired to be removed, more preferably at least 95 wt%, or even more preferably at least "% lost, even better, at least 98 wt.%, and most preferably at least. The #加工" microelectronic device structure as used herein corresponds to substantially removing photoresist after lithography development and failure to pass quality control testing. At least one of an anti-reflective coating (ARC), a buildup containing polyfluorene + w ± mass, a post-etch residue, an electro-mineral copper, and combinations thereof. Alternatively, reprocessing includes removal of 143740.doc • 12- 201022148 Polymer-containing buildup on the back side and/or beveled edge of the microelectronic device structure. Rework can be performed off-site or in-plant. After reprocessing, the microelectronic device structure can be recoated, Baking and re-patterning according to light lithography techniques known in the art. As defined herein, "recycling" is defined as recycling and reuse or reprocessing and reusing micro after removal of material as described herein. Reserved layer of electronic device In this regard, the recycling of the microelectronic device can be reintroduced into the manufacturing process flow 'can be used as a control or test device, or can be used in a non-related process or non-related product. As defined herein, "substantially eliminates" the pit system Refers to a reduction in pitting corrosion as compared to the pit erosion typically observed with the removal of the composition known in the art. Preferably, the degree of pitting is less than 10% of the pitting observed with other removal compositions, More preferably less than 5%, and most preferably less than 2%. It should be understood that the structure of the microelectronic device to be recovered comprises a substrate selected from the group consisting of: bare enamel; polycrystalline germanium; germanium; In/V compound such as gallium nitride , gallium arsenide, indium phosphide; ilmenite; II/IV compound; II/VI compound 'such as CdSe, CdS, ZnS, ZnSe and CdTe; tantalum carbide; sapphire, sapphire upper; carbon; doped glass; Undoped glass; diamond; GeAsSe glass; and combinations thereof, and can be any diameter or thickness conventionally used in the art. For example, substrate diameters used in the art include 200 mm, 300 mm, 4 English, 6 inches, and not The thickness of the 450 mm 300 mm substrate is 750 μηη, and the thickness of other substrates is proportional to the diameter of the 300 mm substrate. The requirements for successful recycling include (but are not limited to) zero or negligible front side, oblique 143740.doc -13- 201022148 Edge, and / or back side Shi Xikeng money; less than 25 particles at 0.2 5 pm, less than 50 particles with 〇12 μηι or less than 100 particles at 0.09 μπι, total thickness variation (TTV Less than about 5 μπι 'surface metal contamination is less than 1χ1〇1〇1 atom cm·2; and/or the thickness of the recovered substrate (without any other retention layer) is within 5% of the initial substrate thickness, preferably within 2% And the best is within 1%. As defined herein, "total thickness variation" corresponds to the absolute difference between the maximum thickness and the minimum thickness of the microelectronic device wafer, as determined by thickness scanning or a series of point thickness measurements as is known in the art. Requirements for successful wafer rework include, but are not limited to, substantially removing photoresist, polymer-containing buildup, and/or electroplated copper from the outermost edges and back sides of the device substrate without substantial damage The layer to be retained, which reduces particle and metal contamination during subsequent processing. The removal of the composition can be embodied in a wide variety of specific formulations, as described in more detail below. In all such compositions, the particular components of the composition are discussed with reference to the range of weight percentages including the lower limit of zero, and it is understood that the components may or may not be present in each particular embodiment of the composition. And, in the presence of such components, the components may be present in a concentration as low as 〇〇〇1% by weight, based on the total weight of the composition using the components. In one aspect, the removal composition (so-called "green" removal composition) that meets national and international environmental standards is described. Diethylene glycol butyl ether and other solvents containing ethyl ether are HAP chemicals and can harm the environment. For example, diethylene glycol butyl ether has a very high chemical oxygen demand (COD) value, which is the mass of oxygen consumed per liter/pool. Due to the high value of diethylene glycol butyl ether, 143740.doc • 14- 201022148 has been banned or restricted to very low levels in various countries. The first aspect of the "green" or "environmentally friendly" removal composition can include an etchant source, at least one interfacial activator, optionally water, optionally at least one organic solvent, optionally at least one organic acid, optionally as appropriate An oxidizing agent, optionally at least one chloride source, optionally at least one chelating agent, and optionally at least one antifoaming agent, which is present in the following ranges based on the total weight of the composition: Component Weight % Money encapsulant about 0.01% Up to about 90% interface activator from about 0.01% to about 15% optional organic solvent from 0 to about 25% optional organic acid from 0 to about 25% optional chelating agent from 0 to about 25% optional oxidizing agent from 0 to about 25% Selective vapor source 0 to about 25% optional antifoam 0 to about 5% water 0 to about 99% The first aspect of the "green" removal composition can comprise at least one etchant, at least one interfacial activator, Depending on the case, depending on the case, at least one organic solvent, optionally at least one organic acid, optionally at least one oxidant, optionally at least one vapor source, optionally at least one chelating agent, and optionally at least one defoaming agent , Essentially consisting of or constituted by those by those. Typically, the etchant source, interfacial activator, optional water, optional organic solvent, optional organic acid, optional oxidizing agent, optionally chloride source, optional chelating agent, and optional antifoaming agent are specific to each other The ratios and amounts may be suitably varied to provide a desirable composition removal effect on materials selected from the group consisting of: surname residue, low-k dielectric material, high-k dielectric material, barrier 143740.doc - 15- 201022148 Wall materials, ferroelectric materials, nitrides, tellurides, oxides, polymer-containing buildups, ARC materials, doped regions, other materials, and combinations thereof; and/or processing equipment, such as familiarity This technology can be easily determined without much effort. In a preferred embodiment, the first aspect of the "green" removal composition is substantially free of amines. As defined herein, "substantially absent" corresponds to less than about 1 wt%, more preferably less than 0.5 wt.%, and most preferably less than wt1 wt.%, based on the total weight of the composition. When diluted with deionized water at 20:1, the pH of the "green" removal composition of the first aspect is from about 〇 to about 7, more preferably from about 2.5 to about 4.5, most preferably from about 3 to about Within the scope of 3.5. The etchant may include, but is not limited to, a fluoride, an amine, and/or a hydroquinone salt, which includes at least one of the following: hydrogen fluoride (HF); xenon difluoride (XeF2); a fluorinated bond (NHJ); Ammonium fluoride (nrj); alkyl hydrogen fluoride (NRHJ); ammonium hydrogen difluoride (nha); dialkyl ammonium hydrogen fluoride (ΝΙΗβ); trialkyl ammonium hydrogen fluoride (nihf); trialkylammonium hydrogen trifluoride (NR_3: 3HF) Anhydrous hydrogen fluoride D to bite complex; anhydrous hydrogen fluoride triethylamine complex 'amine hydrogen fluoride complex' wherein r may be the same or different from each other and selected from the group consisting of linear or branched Ci-C6 alkyl groups ( For example, methyl, ethyl, propyl, butyl, pentyl, hexyl), and wherein the amine includes a linear or branched Ci-Cso alkylamine, a substituted or unsubstituted arylamine, ethylene Alcoholamines, alkanolamines and amines_N_oxides, including but not limited to: pyridine; 2-ethylpyridine; 2-decyloxypyridine and its derivatives, such as 3-methoxy 0-bite , 2-methyl <» ratio D; 〇 咬 derivative; dimethyl hydrazine bite; hexahydro pyridine; piperazine; triethylamine; triethanolamine; ethylamine, methylamine, butyl 143740 .do C -16 · 201022148 Amine, tert-butylamine, tributylamine, dipropylamine, diamine, diethylene glycolamine, early ethanolamine; "比嘻;异"恶唾;1,2,4-三Saliva; η η than bite; squirt bite; ° azine; Jian Hua; 啥 ;; 喧 喧 吲嗓; 吲嗓; 唾 Ν; Ν-methylmorpholine-Ν-oxide (NMMO); tridecylamine-Ν -oxide; triethylamine oxime oxide; ° pyridine-oxime-oxide; Ν-ethylmorpholine-Ν-oxide; Ν-mercaptopyridinium-Ν-oxide; Ν-ethyl' • Bilo bite-Ν-oxide; 1-methylmime; diisopropylamine; diisobutylamine; aniline; aniline derivatives; and combinations thereof. Or 'surnames' may include hydroxide salts including, but not limited to, alkali metal hydroxides, soiled metal hydroxides, quaternary amine hydroxides, and combinations thereof. Preferably the etchant comprises hydrogen fluoride. Interfacial activators contemplated include anions, cations (based on quaternary ammonium cations), and/or zwitterionic interfacial activators. For example, suitable nonionic interfacial activators may include fluoroalkyl interfacial activators, ethoxylated fluoro interface activators, polyethylene glycol, polypropylene glycol, polyethylene glycol ethers or polypropylene glycol shouts, citrates, Dodecylbenzenesulfonic acid or its salt, polyacrylate polymer, dimercaptophenyl polyoxyethylene, polyfluorene oxide or modified polyoxyloxy polymer, ethyl methacrylate or modified acetylene glycol An alkylammonium or modified alkylammonium salt, and an alkylphenol polyglycidyl ether, and a combination comprising at least one of the foregoing. In a preferred embodiment, the nonionic interfacial activator can be an ethoxylated fluorine interfacial activator such as ZONYL® FSO-lOO Fluoride Interface Activator (DuPont Canada, Inc., Mississauga, Ontario, Canada). The anionic interfacial activators contemplated in the compositions of the present invention include, but are not limited to, fluorine interfacial activators such as z〇NYl® UR and ZONYL® FS-62 (DuPont)

Canada a 司’ Mississauga, Ontario, Canada);烧基硫酸 143740.doc 17- 201022148 鈉，例如乙基己基硫酸鈉（NIAPROOF® 08)、烷基硫酸 銨、烷基（C1(rC18)羧酸銨鹽、磺基琥珀酸鈉及其酯，例 如，磺基琥珀酸二辛酯鈉、（C1G-C18)磺酸烷基酯鈉鹽；及 二陰離子項酸鹽界面活化劑D〇wFax™(The Dow Chemical 公司，Midland, Mich·，USA)，例如烷基二苯基氧化物二 磺酸鹽DowFaxTM3B2。預期之陽離子界面活化劑包括烷基 銨鹽，例如十六烷基三曱基溴化銨（CTAB)及十六烷基三 曱基硫酸氫銨。適宜兩性離子界面活化劑包括羧酸銨、硫 酸銨、胺氧化物、N-十二烷基-N、N-二甲基甜菜鹼、甜菜 鹼、磺基甜菜鹼、烷基銨基丙基硫酸鹽、及諸如此類。或 者，界面活化劑可包括水溶性聚合物，其包括（但不限 於）：聚乙二醇（PEG)、聚環氧乙烷（PEO)、聚丙二醇 (PPG)、聚乙烯基吡咯啶酮（PVP)、陽離子聚合物、非離子 聚合物、陰離子聚合物、羥乙基纖維素（HEC)、丙烯醯胺 聚合物、聚（丙烯酸）、羧甲基纖維素（CMC)、羧曱基纖維 素鈉（NaCMC)、羥丙基曱基纖維素、聚乙烯基吡咯啶酮 K30、BIOCARE™ 聚合物、DOW™ 乳膠粉（DLP)、 ETHOCEL™乙基纖維素聚合物、KYTAMERTMPC聚合物、 METHOCEL™纖維素醚、POLYOX™水溶性樹脂、 SoftCATTM 聚合物、UCARETM 聚合物、UCONTM 流體、 PPG-PEG-PPG嵌段共聚物、PEG-PPG-PEG嵌段共聚物、及 其組合。水溶性聚合物可為短鏈或長鏈聚合物且可與本發 明之非離子、陰離子、陽離子、及/或兩性離子界面活化 劑組合。較佳地，界面活化劑包含二陰離子磺酸鹽界面 143740.doc -18- 201022148 活化劑、ppG_peg_pp ^ rru飲段共聚物、pEG ppG_pE(3嵌段共 聚物、及其組合。 、 組σ物中可包括水部分地係因為其溶解氟化物物質之能 力。較佳為去離子水。 .當存在有機_時，其作為溶料助滲透並溶解有機殘 餘物潤濕微電子裝置結構之表面以有利於材料移除及/ 或鈍化下伏晚鄰材料（例如，㈣子裝置基板）。本文預期 之有機溶劑包括（但不限於）醇、醚、吡咯啶酮、二醇、羧 酸、二酵醚、胺、酮、醛、烷烴、烯烴、炔烴及胺，更佳 地醇、醚、吡咯啶酮、二醇、鲮酸、及二醇醚，例如甲 醇、乙醇、異丙醇、丁醇、及更高碳數醇（包括二酵、三 醇等）、2,2,3,3,4,4,5,5-八氟-1-戊醇、111111911_全氟小壬 醇、全氟庚酸、1Η，1Η，7Η-十二氟+庚醇、全氟戊酸、 1Η，1Η，8Η，8Η-十二氟-1，8·辛烷二醇、2,2,3,3,4,4,5,5-八氟- l，6-己院二醇、5H-全氟戊酸、七氟丁酸正丁酯、四氫呋喃 (THF)、Ν-甲基吡咯啶酮（ΝΜΡ)、環己基吡咯啶酮、Ν·辛 基吡咯啶酮、Ν-苯基吡咯啶酮、甲酸甲酯、二甲基甲醯胺 (DMF)、二甲亞砜（DMSO)、四亞甲基砜（環丁颯）、乙醚、 苯氧基-2-丙醇（PPh)、苯丙酮、乳酸乙酯、乙酸乙酯、笨 甲酸乙醋、乙猜、丙嗣、乙·—醇、丙二醇、二1•惡烧、丁内 醋、碳酸丁二酿、碳酸乙二醋、碳酸丙二醋、二丙二醇、 兩親物質（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（即’丁基卡必醇）、三乙二醇單丁 143740.doc 19- 201022148 醚、乙二醇單己醚、二乙二醇單己醚、乙二醇苯醚、丙二 醇甲醚、二丙二醇甲醚（DPGME)、三丙二醇甲醚、二丙二 醇二甲基醚、二丙二醇乙_、丙二醇正丙_、二丙二醇正 丙謎（DPGPE)、三丙二醇正丙_、丙二醇正丁醚、二丙二 醇正丁鍵、三丙二醇正丁驗、丙二醇苯醚、及其組合）、 具支鏈氟化或未氟化醚鍵羧酸（CH3CH2)nCHCH2：)mCOOH， 其中n=l-10且m=l-10)、無支鏈氟化或未氟化醚鍵羧酸 (CH3CH2)nO(CH2)mCOOH，其中 n=i-i〇且 、具支鏈 氟化或未氟化無醚鍵羧酸（CH3(CH2)nCOOH，其中n=l-1〇)、無支鏈氟化或未氟化無醚鍵羧酸（CH3(CH2)nC〇〇H， 其中η-1 -1 〇)、二幾酸、三羧酸、及其組合。此外，溶劑 可包含其他兩親物質，即，含有類似於界面活化劑之親水 及疏水部分二者之物質。疏水性通常可藉由納入由烴基或 氟碳基團組成之分子基團來賦予，且親水性通常可藉由納 入離子或不帶電荷的極性官能團來賦予。較佳地有機溶 劑包含環丁颯、丁基卡必醇、二丙二醇㈣、或其混合 物。 可選額外的酸幫助低妨電材料中交聯聚合物鍵斷裂 溶解。額外㈣可㈣躺及/或無㈣且⑽（但不㈣ 蝴酸、草酸、琥㈣、檸檬酸、乳酸、、 四氣删酸、氫氟酸、氫氣酸、甲酸、富馬酸、㈣氟^, 一酸馬來酸、蘋果酸、L_酒石酸、甲項酸、 酸、碘酸、疏基乙酸、炉代 硫代乙酸乙醇酸、硫酸、璃酸 丙炔酸、丙鲷酸、乙醯乙酸、及其組合。 143740.doc •20· 201022148 可添加螯合劑以減少或消除晶圓回收期間裝置表面上之 金屬污染物。本文預期之螯合劑包括（但不限於）：β-二丙 酮酸鹽化合物’例如乙醯丙酮酸鹽、1，1，1-三氟-2,4·戊二 酮、及1，1，1,5,5,5-六氟-2,4-戊二酮；羧酸酯，例如甲酸酯 及乙酸酯及其他長鏈羧酸酯；及醯胺（及胺），例如雙（三甲 基甲矽烷基醯胺）四聚體。額外螯合劑包括胺及胺基酸 (即’甘胺酸、絲胺酸、脯胺酸、亮胺酸、丙胺酸、天冬 醯胺、天冬胺酸、麵胺醯胺、纈胺酸、及離胺酸）、檸檬 酸、乙酸、馬來酸、草酸、丙二酸、琥珀酸、膦酸、膦酸 衍生物（例如羥基亞乙基二膦酸（HEDP)、1-羥基乙烷-1，1-二膦酸、氮基-叁（亞甲基膦酸））、氮基三乙酸、亞胺基二 乙酸、依替膦酸（etidronic acid)、乙二胺、乙二胺四乙酸 (EDTA)、及（1，2-伸環己基二氮基）四乙酸（CDTA)、尿酸、 四乙醇二曱醚、五曱基二伸乙基三胺（PMDETA)、1，3,5-三 嗪-2,4,6-三硫醇三鈉鹽溶液、1，3,5-三嗪-2,4,6-三硫醇三敍 鹽溶液、二乙基二硫代胺基曱酸納、經二取代之二硫代胺 基甲酸鹽（RiCCHe^OhNI^CSzNa，其具有一個烷基（R2= 己基、辛基、癸基或十二烷基）及一個募醚 (R^C^C^O)2，其中Rk乙基或丁基））、硫酸銨、單乙醇 胺（MEA)、Dequest 2000、Dequest 2010、Dequest 2060、 二伸乙基三胺五乙酸、丙二胺四乙酸、2-羥基吡咬ι_氧化 物、乙二胺二琥珀酸、三磷酸五鈉、及其組合。不像可能 需要與鹼結合以形成能夠螯合的去質子化化合物的未氣化 β·二酮一樣，氟化β-二酮螯合劑可在無鹼的情況下使用。 143740.doc -21 - 201022148 螯合劑可在製造商處、在組合物引入裝置晶圓之前或者在 裝置晶圓處（即’在現場）引入組合物中。進一步預期，除 螯合劑以外，其他組份可添加於組合物中以稀釋、維持 及/或增加組合物中其他組份之濃度。較佳地，螯合劑包 含至少一種膦酸衍生物。 本文預期之氧化劑包括（但不限於）過氧化氫（H202)、 FeCh(水合及未水合二者）' 過硫酸氫_製劑（〇x〇ne) (2KHS05*KHS〇4.K2S〇4)、按多原子鹽（polyatomic salt)(例 如’過氧單硫酸銨、亞氣酸銨（NH4C1〇2)、氣酸銨 (NH4Ci〇3)、碘酸銨（nh4io3)、過硼酸銨（nh4bo3)、高氣 酸銨（NHUCIO4)、高碘酸銨（NH4I〇3)、過硫酸銨 ((NH4)2S208)、次氣酸銨（nh4cio))、鈉多原子鹽（例如， 過硫酸鈉（NasSzOs)、次氣酸鈉（NaCIO))、鉀多原子鹽（例 如，碘酸鉀（KIO3)、高錳酸鉀（ΚΜη04)、過硫酸鉀、硝酸 (hno3)、過硫酸钟（k2S208)、次氣酸鉀（KCIO))、四甲基銨 多原子鹽（例如，四甲基亞氣酸銨（(N(CH3)4)C102)、四甲 基氣酸銨（(N(CH3)4)Cl〇3)、四甲基碘酸銨（(N(CH3)4)I〇3)、 四甲基過硼酸銨（(N(CH3)4)B〇3)、四甲基高氯酸銨 ((N(CH3)4)C104)、四甲基高碘酸銨（(n(ch3)4)io4)、四甲基 過硫酸銨（(N(CH3)4)S2〇8))、四丁基銨多原子鹽（例如，四 丁基過氧單硫酸銨）、過氧單硫酸、硝酸鐵（Fe(N〇3)3)、過 氧化氫脲（(co(nh2)2)h2o2)、過乙酸（CH3(CO)〇〇H)、及其 組合。氧化劑可在製造商處、在將組合物引入裝置晶圓之 月1J、或者在裝置晶圓處（即，在現場）引入組合物中。較佳 143740.doc •22· 201022148 地，氧化劑包含過氧化物化合物。 此項技術中已知’ HF在金屬污染物（包括銅）之存在下造 成微電子裝置基板（包括矽）之坑蝕。為實質上消除此有害 坑姓效應’可將範化物源添加於移除組合物中以在回收製 程期間使微電子裝置基板之坑蝕降至最低，該等氯化物源 可為例如（但不限於）氫氣酸、驗金屬氣化物（例如，NaC1、 KCo、RbC卜CsCl等）、鹼土金屬氣化物（例如，MgCl2、 CaCl2、SrCl2、BaCl2等）、氣化铵、具有式Nr1r2r3r4c12 烷基氯化銨（其中R1、R2、R3及R4可彼此相同或不同且可 為Η或具支鏈或直鏈CkC6烷基（例如，甲基、乙基、丙 基、丁基、戊基或己基））及其組合。較佳地，氣化物源包 含氯化敍。 消泡劑係引發溶液中之泡沫快速将塌或抑制起泡程度之 物質。較佳地，消泡劑必須滿足三個條件：其應不溶於溶 液，其應具有正鋪展係數，且其應具有正進入係數。預期 消泡劑通常包括（但不限於）基於聚矽氧油、基於礦物油、 基於天然油、基於乙炔系及基於碟酸酯之消泡劑。更佳 地，消泡劑包括（但不限於）環氧乙烷/環氧丙烷嵌段共聚 物’例如Pluronic®(BASF®)產品（例如，plur〇nic®17R2、Canada a Division 'Mississauga, Ontario, Canada); sulphuric acid sulphate 143740.doc 17- 201022148 Sodium, such as sodium hexyl sulphate (NIAPROOF® 08), ammonium alkyl sulphate, alkyl (C1 (rC18) carboxylic acid ammonium salt Sodium sulfosuccinate and esters thereof, for example, sodium dioctyl sulfosuccinate, sodium (C1G-C18) sulfonate; and dianionic acid salt interface activator D〇wFaxTM (The Dow Chemical Company, Midland, Mich., USA), for example alkyl diphenyl oxide disulfonate DowFaxTM 3B 2. The intended cationic interfacial activator includes alkyl ammonium salts such as cetyltridecyl ammonium bromide (CTAB) And cetyltridecyl ammonium hydrogen sulfate. Suitable zwitterionic interface activators include ammonium carboxylate, ammonium sulfate, amine oxides, N-dodecyl-N, N-dimethyl betaine, betaine , sulfobetaine, alkyl ammonium propyl sulfate, and the like. Alternatively, the interfacial activator may comprise a water soluble polymer including, but not limited to: polyethylene glycol (PEG), polyethylene oxide Alkane (PEO), polypropylene glycol (PPG), polyvinylpyrrolidone (PVP), cationic polymer Nonionic polymer, anionic polymer, hydroxyethyl cellulose (HEC), acrylamide polymer, poly(acrylic acid), carboxymethyl cellulose (CMC), sodium carboxymethyl cellulose (NaCMC), hydroxypropyl Base-based cellulose, polyvinylpyrrolidone K30, BIOCARETM polymer, DOWTM latex powder (DLP), ETHOCELTM ethyl cellulose polymer, KYTAMERTM PC polymer, METHOCELTM cellulose ether, POLYOXTM water soluble Resins, SoftCATTM Polymers, UCARETM Polymers, UCONTM Fluids, PPG-PEG-PPG Block Copolymers, PEG-PPG-PEG Block Copolymers, and combinations thereof. Water-soluble polymers can be short-chain or long-chain polymers And may be combined with the nonionic, anionic, cationic, and/or zwitterionic interfacial activators of the present invention. Preferably, the interfacial activator comprises a dianion sulfonate interface 143740.doc -18- 201022148 activator, ppG_peg_pp ^ rru Drinking segment copolymer, pEG ppG_pE (3 block copolymer, and combinations thereof. Group σ may include water in part because of its ability to dissolve fluoride species. Deionized water is preferred. When organic is present _ When it Permeating the dissolution and dissolving the organic residue to dissolve the surface of the microelectronic device structure to facilitate material removal and/or passivation of the underlying material (eg, (iv) sub-device substrate). The organic solvents contemplated herein include (but Not limited to) alcohols, ethers, pyrrolidone, diols, carboxylic acids, diethanol ethers, amines, ketones, aldehydes, alkanes, alkenes, alkynes and amines, more preferably alcohols, ethers, pyrrolidone, diols, Capric acid, and glycol ethers such as methanol, ethanol, isopropanol, butanol, and higher carbon alcohols (including di-fermented, triol, etc.), 2, 2, 3, 3, 4, 4, 5, 5-octafluoro-1-pentanol, 111111911_perfluoro behenyl alcohol, perfluoroheptanoic acid, 1 hydrazine, 1 hydrazine, 7 fluorene-dodecyl fluoride/heptanol, perfluoropentanoic acid, 1 Η, 1 Η, 8 Η, 8 Η- 十Difluoro-1,8.octanediol, 2,2,3,3,4,4,5,5-octafluoro-l,6-hexadiol, 5H-perfluoropentanoic acid, heptafluorobutane N-butyl acrylate, tetrahydrofuran (THF), Ν-methylpyrrolidone (oxime), cyclohexyl pyrrolidone, anthracene octyl pyrrolidone, fluorenyl-phenylpyrrolidone, methyl formate, dimethyl Formamide (DMF), dimethyl sulfoxide (DMSO), tetramethylene sulfone (cyclobutane), Ether, phenoxy-2-propanol (PPh), phenylacetone, ethyl lactate, ethyl acetate, ethyl formate, acetonitrile, acetamidine, ethyl alcohol, propylene glycol, diacetonate Internal vinegar, dibutyl carbonate, ethylene carbonate, propylene carbonate, dipropylene glycol, amphiphilic substances (diethylene glycol monomethyl ether, triethylene glycol monomethyl ether, diethylene glycol monoethyl ether, triethyl Glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, diethylene glycol monobutyl ether (ie 'butyl carbitol'), triethylene glycol monobutyl 143740.doc 19- 201022148 ether, Ethylene glycol monohexyl ether, diethylene glycol monohexyl ether, ethylene glycol phenyl ether, propylene glycol methyl ether, dipropylene glycol methyl ether (DPGME), tripropylene glycol methyl ether, dipropylene glycol dimethyl ether, dipropylene glycol B_, Propylene glycol, n-propyl propylene glycol, dipropylene glycol, propylene glycol (DPGPE), tripropylene glycol, n-propyl propylene glycol, n-butyl propylene glycol, n-butylene glycol, n-propylene glycol, n-butylene glycol, n-propane diol, propylene glycol phenyl ether, and combinations thereof, branched-chain fluorine Or non-fluorinated ether linkage carboxylic acid (CH3CH2)nCHCH2:)mCOOH, where n = l-10 and m = l-10), unbranched fluorinated or unfluorinated ether linkage carboxylic acid (CH3CH2) nO(CH2)mCOOH, wherein n=ii〇, branched-chain fluorinated or unfluorinated ether-free carboxylic acid (CH3(CH2)nCOOH, where n=l-1〇), unbranched fluorinated or not Fluorinated ether-free carboxylic acid (CH3(CH2)nC〇〇H, wherein η-1 -1 〇), diacid, tricarboxylic acid, and combinations thereof. In addition, the solvent may contain other amphiphilic materials, i.e., materials containing both hydrophilic and hydrophobic moieties similar to the interfacial activator. Hydrophobicity can generally be imparted by incorporating a molecular group consisting of a hydrocarbyl group or a fluorocarbon group, and the hydrophilicity can usually be imparted by the inclusion of an ionic or uncharged polar functional group. Preferably, the organic solvent comprises cyclobutyl hydrazine, butyl carbitol, dipropylene glycol (tetra), or a mixture thereof. An optional additional acid helps break the cross-linking polymer bond in the low-lying electrical material. Additional (iv) may (four) lie and / or no (four) and (10) (but not (four) oleic acid, oxalic acid, amber (tetra), citric acid, lactic acid, tetragas acid, hydrofluoric acid, hydrogen acid, formic acid, fumaric acid, (four) fluorine ^, monoacid maleic acid, malic acid, L_tartaric acid, methylic acid, acid, iodic acid, thioglycolic acid, thioacetic acid glycolic acid, sulfuric acid, lanolic acid, propionic acid, acetamidine Acetic acid, and combinations thereof. 143740.doc •20· 201022148 A chelating agent may be added to reduce or eliminate metal contaminants on the surface of the device during wafer recovery. The chelating agents contemplated herein include, but are not limited to, β-dipyruvate Salt compounds such as acetoacetate, 1,1,1-trifluoro-2,4·pentanedione, and 1,1,1,5,5,5-hexafluoro-2,4-pentanedione Carboxylates, such as formates and acetates and other long chain carboxylates; and guanamines (and amines), such as bis(trimethylformamidine) tetramers. Additional chelating agents include amines And amino acids (ie, 'glycine, serine, valine, leucine, alanine, aspartame, aspartic acid, acetoamine, valine, and lysine) ,lemon , acetic acid, maleic acid, oxalic acid, malonic acid, succinic acid, phosphonic acid, phosphonic acid derivatives (such as hydroxyethylidene diphosphonic acid (HEDP), 1-hydroxyethane-1,1-diphosphonic acid, Nitrogen-germanium (methylene phosphonic acid), nitrogen triacetic acid, iminodiacetic acid, etidronic acid, ethylenediamine, ethylenediaminetetraacetic acid (EDTA), and (1, 2-cyclohexyldiazepine)tetraacetic acid (CDTA), uric acid, tetraethanol dioxime ether, pentadecyl diethylidene triamine (PMDETA), 1,3,5-triazine-2,4,6 - trithiol trisodium salt solution, 1,3,5-triazine-2,4,6-trithiol triazine salt solution, diethyldithioamino phthalate sodium, disubstituted disulfide a carbamic acid formate (RiCCHe^OhNI^CSzNa, having an alkyl group (R2 = hexyl, octyl, decyl or dodecyl) and an ether (R^C^C^O)2, wherein Rk ethyl or butyl)), ammonium sulfate, monoethanolamine (MEA), Dequest 2000, Dequest 2010, Dequest 2060, di-ethyltriamine pentaacetic acid, propylenediaminetetraacetic acid, 2-hydroxypyrimidine , ethylenediamine disuccinic acid, pentasodium triphosphate, and combinations thereof. Like the unvaporized β-diketone which may be required to combine with a base to form a deprotonated compound capable of chelation, the fluorinated β-diketone chelating agent can be used without a base. 143740.doc -21 - 201022148 The chelating agent can be introduced into the composition at the manufacturer, prior to introduction of the composition into the device wafer, or at the device wafer (i.e., at the site). It is further contemplated that in addition to the chelating agent, other ingredients may be added to the composition to dilute, maintain, and/or increase the concentration of other components in the composition. Preferably, the chelating agent comprises at least one phosphonic acid derivative. The oxidizing agents contemplated herein include, but are not limited to, hydrogen peroxide (H202), FeCh (both hydrated and unhydrated) 'hydropersulfate _ formulation (〇x〇ne) (2KHS05*KHS〇4.K2S〇4), According to polyatomic salt (for example, 'peroxymonoammonium monosulfate, ammonium sulfite (NH4C1〇2), ammonium oxychloride (NH4Ci〇3), ammonium iodate (nh4io3), ammonium perborate (nh4bo3), Ammonium oleate (NHUCIO4), ammonium periodate (NH4I〇3), ammonium persulfate ((NH4)2S208), ammonium hyaluronate (nh4cio), sodium polyatomic salt (eg, sodium persulfate (NasSzOs) , sodium hypogasate (NaCIO), potassium polyatomic salt (for example, potassium iodate (KIO3), potassium permanganate (ΚΜη04), potassium persulfate, nitric acid (hno3), persulfate clock (k2S208), secondary gas Potassium acid (KCIO)), tetramethylammonium polyatomic salt (for example, tetramethylammonium sulphate ((N(CH3)4)C102), tetramethylammonium sulphate ((N(CH3)4)Cl) 〇3), ammonium tetramethyl iodate ((N(CH3)4)I〇3), tetramethylammonium perborate ((N(CH3)4)B〇3), tetramethylammonium perchlorate ( (N(CH3)4)C104), tetramethylammonium periodate ((n(ch3)4) io4), tetramethylammonium persulfate ((N(CH3)4)S2〇8)), Butyl ammonium polyatomic salt (for example, tetrabutylammonium monooxymonosulfate), peroxymonosulfuric acid, ferric nitrate (Fe(N〇3)3), hydrogen peroxide urea ((co(nh2)2)h2o2) Peracetic acid (CH3(CO)〇〇H), and combinations thereof. The oxidant can be introduced into the composition at the manufacturer, at the time of introducing the composition into the device wafer, or at the device wafer (i.e., at the site). Preferably, 143740.doc • 22· 201022148, the oxidizing agent comprises a peroxide compound. It is known in the art that HF causes pitting of microelectronic device substrates (including germanium) in the presence of metal contaminants, including copper. In order to substantially eliminate this deleterious pit last effect, a source of vanishing material may be added to the removal composition to minimize pit erosion of the substrate of the microelectronic device during the recycling process, such as (but not Limited to) hydrogen acid, metal gasification (eg, NaC1, KCo, RbC, CsCl, etc.), alkaline earth metal vapor (eg, MgCl2, CaCl2, SrCl2, BaCl2, etc.), ammonium sulfate, chlorinated with the formula Nr1r2r3r4c12 Ammonium (wherein R1, R2, R3 and R4 may be the same or different from each other and may be hydrazine or a branched or linear CkC6 alkyl group (for example, methyl, ethyl, propyl, butyl, pentyl or hexyl)) And their combinations. Preferably, the vapor source comprises a chloride. An antifoaming agent is a substance that initiates a rapid collapse or inhibition of foaming in a solution. Preferably, the antifoaming agent must satisfy three conditions: it should be insoluble in the solution, it should have a positive spreading factor, and it should have a positive entry coefficient. Antifoaming agents are generally contemplated to include, but are not limited to, polyoxyphthalocyanine based, mineral based, natural oil based, acetylene based, and dish ester based defoamers. More preferably, the antifoaming agent includes, but is not limited to, an ethylene oxide/propylene oxide block copolymer such as a Pluronic® (BASF®) product (e.g., plur〇nic® 17R2)

Pluronic®17R4、Pluronic®3 1Rl 及 pluronic®25R2);醇烷 氧基化物，例如Plurafac®產品（BASF®)(例如， Plurafac®PA20);脂肪醇烧氧基化物，例如Surfonic® (Huntsmen)(例如，Surfonic®Pl);填酸醋與非離子乳化劑 之摻合物’例如消泡劑M(Ortho Chemicals Australia Pty.公 143740.doc -23- 201022148 司）及超級消泡劑225(Varn Products);及其組合。注意， 消泡劑Μ亦可作為潤濕劑，且因此當使用消泡劑Μ時其可 為界面活化劑及消泡劑二者。此外，二乙二醇单丁鱗、丙 一醇曱謎、二丙二醇甲謎（DPGME)、三丙二醇曱鍵、二丙 二醇二甲基醚、二丙二酵乙謎、丙二醇正丙醚、二丙二 醇正丙醚（DPGPE)、三丙二醇正丙謎、丙二酵正丁醚、二 丙二醇正丁醚、三丙二醇正丁醚、丙二醇苯醚、及丙二醇 可單獨使用或與其他消泡劑組合使用以有效消除泡沫。在 一個實施例中’消泡劑選自由環氧乙烷/環氧丙烷嵌段共 聚物、醇烷氧基化物、脂肪醇烷氧基化物、磷酸酯與非離 子乳化劑之摻合物、及其組合組成之群。在另一實施例 中，消泡劑選自由環氧乙烷/環氧丙烷嵌段共聚物、醇烷 氧基化物、脂肪醇烷氧基化物、及其組合組成之群。在再 實鞑例中，消泡劑為環氧乙烷/環氧丙烷嵌段共聚物。 鑒於第一態樣之「綠色」移除組合物之性質，組合物較 佳實質上不存在包括伸乙基(例如，#乙基、二伸乙基、 伸乙基等）之有機溶劑及其他ΗΑρ有機溶劑。舉例而 言，若存在有機溶劑，則其較佳包括伸丙基及/或丙二醇 應瞭解，包括含伸乙基之溶劑的組合物亦係可能的， 如由熟悉此項技術者容易地確定。 該等組合物可視情況 及非活性成份，例如， 劑、PH穩定劑等。 在較佳實施例中，第 包括額外組份，其包括活性成份以 流變劑、穩定劑、鈍化劑、分散 一態樣之「綠色」移除組合物包含 143740.doc •24· 201022148 至少一種餘刻劑、至少一種界面活化劑、水、及至少一種 消泡劑，由該等構成或基本上由該等構成。在又一較佳實 施例中，第一態樣之「綠色」移除組合物包含至少一種姓 刻劑、至少一種界面活化劑、水、及至少一種消泡劑，由 該等構成或基本上由該等構成，其中該消泡劑包含選自由 以下組成之群之物質：環氧乙烷/環氧丙烷嵌段共聚物、 醇烧氧基化物、脂肪醇烧氧基化物、碟酸酯與非離子乳化 劑之摻合物、及其組合。在另一較佳實施例中，第一態樣 之「綠色」移除組合物包含至少一種蝕刻劑、至少一種界 面活化劑、水、至少一種消泡劑、至少一種氣化物源、及 至少一種螯合劑’由該等構成或基本上由該等構成。在另 一實施例中，第一態樣之「綠色」移除組合物包含至少一 種蝕刻劑、至少一種界面活化劑、水、至少一種消泡劑、 至種氣化物源、及至少一種螯合劑，由該等構成或基 本上由該等構成，其中該消泡劑包含選自由以下組成之群 之物質：環氧乙烷/環氧丙烷嵌段共聚物、醇烷氧基化 物、脂肪醇烷氧基化物、磷酸酯與非離子乳化劑之摻合 物'及其組合。在再一較佳實施例中，第一態樣之「綠 色」移除組合物包含至少一種蝕刻劑、至少一種界面活化 劑、水、至少一種消泡劑、至少一種氣化物源、至少一種 氧化劑及至少—種螯合劑’由該等構成或基本上由該等構 成。在另-較佳實施例中，第一態樣之「綠色」移除組合 物包含至少一種蝕刻劑、至少一種界面活化劑、水、至少 種/肖泡劑、至少一種氣化物源、至少一種氧化劑及至少 143740.doc •25- 201022148 一種螯合劑，由該等構成或基本上由該等構成，其中該消 泡劑包含選自由以下組成之群之物質：環氧乙烷/環氧丙 烷嵌段共聚物、醇烷氧基化物、脂肪醇烷氧基化物、填酸 酯與非離子乳化劑之摻合物、及其組合。舉例而言，第一 態樣之移除組合物可包含水、氯化錢、HF、膦酸衍生物整 合劑、烷基二苯基氧化物二磺酸鹽界面活化劑及環氧乙 烧/環氧丙燒嵌段共聚物消泡劑，由該等構成或基本上由 該等構成。第一態樣之移除組合物的另一實例包含水、氣 化鍵、HF、HEDP、烷基二苯基氧化物二磺酸鹽界面活化 劑及環氧乙烷/環氧丙烷嵌段共聚物消泡劑，由該等構成 或基本上由該等構成。氧化劑（例如過氧化氫）可在製造商 處、在組合物引入裝置晶圓之前或者在裝置晶圓處（即， 在現場）引入組合物中。 第一態樣之「綠色」移除組合物可進一步包括選自由以 下組成之群之材料殘餘物：蝕刻後殘餘物、低_k介電材 料、金屬堆疊材料、高吨介電材料、障壁層材料、鐵電材 料、氮化物、矽化物、氧化物、含聚合物之累積物、arc 材料、經摻雜區域、其他材料、及其組合。較佳地，該等 材料溶解於及/或懸浮於「綠色」移除，組合物中且移除組 合物仍具有其期望用途。 在一個實關巾，第-H樣之「綠色」移雜合物調配 成以下濃縮實施例，其中所有百分比均基於調配物之總重 量以重量計： 143740.doc -26- 201022148 組份 重量％ 較佳(重量％) 最佳(重量％) HF 約0.01%至約90% 約2%至約75% 約5%至約30% 界面活性劑 約0.01%至約15% 約0.1%至約5% 約0.5%至約4% 有機溶劑 〇至約25% 0%至約10% 0%至約10% 整合劑 〇至約25% 約0.1 %至約20% 約2%至約10% 氣化物源 _ 〇至約25% 約0.1%至約10% 約1 %至約10% 消泡劑 〇至約5% 約0.01 %至約3% 約0.01%至約1% 水 0〇/〇 至 99% 約5%to 90% 約10%至70% 濃縮實施例可包括約〇·〇1%至約20%、更佳約1%至約15 重量％的至少—種氧化劑，其可預先添加及/或在移除現場 添加°當存在時，有機溶劑及/或有機酸之下限以調配物 之總重量計可為0.01重量❶/。。在尤其較佳實施例中，該等 組份之重量百分比的範圍為：相對於純淨界面活化劑，約 1:1至約10:1純淨氣化物源、較佳約2:i至約5:1、且最佳約 3.1至約4:1 ;相對於純淨界面活化劑，約1:1至約15:1純淨 HF、較佳約3:1至約1〇:1、且最佳約7:1至約8:i ;相對於純 淨界面活化劑，約1:1至約10:1純淨螯合劑、較佳約2:1至 約8:1、且最佳約4:1至約5:1 ;且相對於純淨界面活化劑， 約〇.01:1至約0.15:1純淨消泡劑、較佳約0.03:1至約 〇.12:1、且最佳約 0.06:1 至約 〇.〇9:1。 在第一態樣之各實施例中’移除組合物可實質上不存在 以下物質中的至少一者：硝酸、硫酸、内醯胺（例如，六 氫°比咬酮及/或吡咯啶酮）、超臨界流體、胺及藉由至少一 種搭與至少一種芳族化合物縮聚製得之聚合物。 在一個實施例中，第一態樣之移除組合物係用於回收微 電子袋置結構。換言之，可自微電子裝置結構移除一個可 143740.doc -27- 201022148 移除層或一個以上的可移除層。 在另一實施例中，第一態樣之移除組合物可用於再加工 微電子裝置結構，由此移除該結構之背侧及/或斜邊緣上 的含聚合物之累積物。自結構之背側及/或斜邊緣移除含 聚合物之累積物的方法可需要（但非必需）保護結構之前側 免於暴露於組合物。此一方法可包括將結構定位於單一晶 圓工具上，該工具使用惰性氣體（例如，氮）及/或去離子水 喷射保護晶圓之前側。或者，可藉由在前側上沈積厚光阻 劑層或其他保護性塗層聚合物來保護前側。換言之，若結 構之前側包括當清潔背側及/或斜邊緣時不能暴露於第一 態樣之移除組合物之圖案化及/或毯覆材料時，則應對前 側進行保護。在另一實施例中，將前側與背側/斜邊緣二 者均暴露於第一態樣之移除組合物以同時將材料自前側 (例如，低-k介電材料等）及背側/斜邊緣（例如，含聚合物 之累積物及含銅材料）移除。 使用本文所述之移除組合物移除之低-k介電材料包括 CORAL™、黑金剛石TM(以下稱為BD)、CORAL之衍生 物、BD之衍生物、AURORA®、AURORA®之衍生物、 SiCOH等。如本文所用，「CORAL之衍生物」及「BD之 衍生物」分別對應於使用替代、通常專有之沈積方法沈積 之CORAL及BD材料。利用不同處理技術將產生分別不同 於CORAL™及BLACK 01八140仙1^之€：01^1^及80材料。 在本發明第一態樣之另一實施例中，將銅離子添加於移 除組合物中以加速鎢及含鎢層自微電子裝置結構之移除。 143740.doc -28 · 201022148 當存在時，所添加銅離子之量以組合物之總重量計可在約 0.01 wt%至約5 wt%、較佳約〇. 1 wt%至約2 · 5 wt%、且最佳 約0.2 wt%至約1 wt%之範圍内。 在第二態樣中，闡述另一種「綠色」或環境友好移除組 合物，該移除組合物包含钱刻劑源、至少一種界面活化 劑、水、及視情況至少一種氧化劑，由該等構成或基本上 由該等構成。移除組合物之組份以組合物之總重量計以以 下範圍存在： 組份 重量％ ϋ刻劑 約0.01 %至約90% 界面活化劑 約0.01%至約15% 水 約 0.01% 至約 99.98% 氧化劑 0至約10% 用於第二態樣之移除組合物的蝕刻劑及可選氧化劑包括 彼等以上針對第一態樣之移除組合物所闡述者。適於第二 態樣之移除組合物的界面活化劑包括（但不限於）：陰離子 界面活化劑，例如十二烷基苯磺酸（DDBSA)或其鹽、其他 直鏈烷基苯磺酸（LABSA)或其鹽、烷氧基化脂肪醇之磷酸 酯（例如，KLEARFAC® AA270，由BASF公司出售）；非離 子界面活化劑，例如壬基盼乙氧基化物（例如，Tergitol™ 15-S-9，自DOW購得）、脂肪醇烷氧基化物（例如Surfonic® (Huntsmen)(例如，Surfonic®Pl))、聚氧乙烯二醇十二烧 基謎（例如，Brij 35)、及醇烧氧基化物（例如Plurafac®產品 (BASF®)(例如’ Plurafac®PA20));聚合物界面活化劑， 例如PPG-PEG-PPG嵌段共聚物、PEG-PPG-PEG嵌段共聚 143740.doc -29- 201022148 物、環氧乙烷/環氧丙烷嵌段共聚物，例如piur〇nic⑧ (BASF®)產品（例如 ’ piuronic®i7R2、Pluronic®17R4、 Pluronic®31Rl 及 Pluronic®25R2);及其組合。較佳地，界 面活化劑包含環氧乙烷/環氧丙烷嵌段共聚物。 該等組合物可視情況包括額外組份，其包括活性成份以 及非活性成份’例如流變劑、穩定劑、鈍化劑、分散劑、 pH穩定劑、消泡劑、氣化物源、氧化劑、螯合劑、共溶劑 等0 第一態樣之「綠色」移除組合物可進一步包括選自由以 下組成之群之材料殘餘物：蝕刻後殘餘物、低·k介電材 料、高-k介電材料、SiCN、含鋁材料、障壁層材料、鐵電 材料、氮化物、矽化物、氧化物、光阻劑、含聚合物之累 積物、ARC材料、經摻雜區域、其他材料、及其組合。較 佳地，該等材料溶解於及/或懸浮於「綠色」移除組合物 中且移除組合物仍具有其期望用途。 #於第二態樣之「綠色」移除組合物之性f，組合物較 佳實質上不存在：包括伸乙基（例如，伸乙基、-伸乙 基、三伸乙基等）之有機溶劑及其他HAp有機溶劑；硝 酸；硫酸；内醯胺（例如，六氫吡啶酮及/或吡咯啶酮）；超 臨界流體；胺；氟化銨；及藉由至少—種醛與至少一種芳 族化合物縮聚製得之聚合物。 在-個實施例中，將第二態樣之「綠色」或環境友好移 除組合物調配成以下濃縮實施例，其中 汀有百分比均基於 調配物之總重量以重量表示： 143740.doc •30· 201022148 組份 重量％ 較佳(重量％) 最佳(重量％) HF 約0.01%至約90% 約2%至約50% 約15%至約25% 界面活性劑 約0.01 %至約15% 約0.1 %至約10% 約2%至約8% 水 0.01% 至99.98% 約10%至95% 約65%至85% 在尤其較佳實施例中，第二態樣之移除組合物包括約17 wt%至約23 wt% HF、約4 wt%至約6 wt%界面活化劑及約 70 wt%至約80 wt%水，其中所有百分比均基於調配物之總 重量以重量表示。當存在時，氧化劑之量較佳在約〇.〇1 wt%至約10 wt%之範圍内。在尤其較佳實施例中，該等組 份之重量百分比範圍為：相對於純淨界面活化劑為約1:1 至約10:1純淨HF、較佳約2:1至約6:1、且最佳約3:1至約 5:1。 第二態樣之移除組合物的較佳實施例包含HF、PEG-PPG-PEG嵌段共聚物及水，由該等構成或基本上由該等構 成。在另一較佳實施例中，第二態樣之移除組合物包含 HF、PPG-PEG-PPG嵌段共聚物及水，由該等構成或基本 上由該等構成。在另一較佳實施例中，第二態樣之移除組 合物包含HF、聚氧乙烯二醇十二烧基醚界面活化劑及水， 由該等構成或基本上由該等構成。氧化劑（例如過氧化氫） 可在製造商處、在組合物引入裝置晶圓之前或者在裝置晶 圓處（即，在現場）引入組合物中。在另一較佳實施例中， 第二態樣之組合物進一步包括至少一種消泡劑。 在一個實施例中，第二態樣之移除組合物用於回收微電 子裝置結構。換言之，可自微電子裝置結構移除一個可移 143740.doc -31 - 201022148 除層或一個以上的可移除層。在另一實施例中，第二態樣 之移除組合物可用於再加工微電子裝置結構，由此移除該 結構之背側及/或斜邊緣上的含聚合物之累積物，如以I 關於第一態樣所述。 應注意，在移除組合物即將與微電子裝置接觸時，第一 與第二態樣之移除組合物應實質上沒有C M p處理期間通常 所用之磨蝕材料。 本文所述移除組合物有效同時自微電子裝置表面移除以 下至少一者：含聚合物之累積物、金屬堆疊材料、低介 電層、高-k介電層、㈣終止層、氮化物、石夕化物、氧化 物、障壁層、光阻劑、_後殘餘物、其他材料、經換雜 區域（不同於經摻雜磊晶Si)及/或其他材料。舉例而言，移 除組合物可自微電子裝置之前侧有效移除低呔介電材料， 同時自微電子I置之背侧及/或斜邊緣移除聚合物及其他 材料，如由熟悉此項技術者所容易地確定。因此，當實施 微電子裝置製造作業時，本文所述之移除組合物可在單一 回收或再加工步驟中有效用於自微電子裝置結構移除至少 一種選自由以下組成之材料以再循環利用及/或再使用該 等結構：低-k介電材料、高斗介電材料、蝕刻終止層、金 屬堆疊材料、氮化物、碎化物、氧化物、光阻劑、障壁 其他材料、經摻雜區 本文所述移除組合物 層、含聚合物之累積物、鐵電材料、 域（不同於經摻雜磊晶Si)及其組合。 滿足回收要求，其包括（但不限於）·· G25 μπ1的粒子少於25 個、0.12 μιη的粒子少於5〇個、或〇 〇9 μϊη的粒子少於1〇〇 143740.doc -32- 201022148 個，總厚度變化（TTV)小於約5 μιη(不需要移除後平坦化製 程）’表面金屬污染小於lx 1〇10個原子cm-2 ;及/或所回收基 板之厚度（無任何其他保留層）在初始基板厚度的5%以内， 較佳在2%以内，且最佳在1%以内；以及再加工/清潔要 求。此外，由於低TTV ’故在再使用之前可能不需要化學 機械拋光（CMP)步驟，該步驟係典型的通用回收實踐， 即’以在濕移除材料之後平坦化基板來平坦化晶圓之前側 或背側。或者’可改變CMP步驟之參數以使能量需要實質 上降低，例如’拋光時間之長度縮短等。最佳地，在自微 電子裝置基板移除材料之後，TTV小於3%、更佳地小於 1 %且最佳小於0.5%。 本文所述之移除組合物亦滿足再使用要求，例如，實現 自裝置基板之最外邊緣及背側實質移除光阻劑、含聚合物 之累積物及/或電鍍銅而不會實質損壞欲保留之層。不像 先前技術（例如，物理拋光邊緣、乾電漿蝕刻、燃燒等）之 再使用組合物一樣，欲自微電子裝置結構移除之至少一種 材料可利用濕溶液移除。 藉由簡單添加各個成份並將其混合至均相狀態來容易地 調配本文所述移除組合物。另外，可容易地將移除組合物 調配成單一包裝調配物或在使用時混合之多份調配物。多 份調配物之個別部分可在工具處或在工具上游之儲存罐中 或二者中混合。在移除組合物中各個成份之濃度可以特定 倍數大幅度變化，例如更稀或更濃，且應理解移除址合物 可不同地或選擇性地包含符合本文揭示内容之各成份的任 143740.doc •33- 201022148 何組合、由其組成或基本由其組成。 因此另態樣係關於本文所述組合物具有少量水及/ 或溶劑、或者另—選擇沒有水及/或溶劑之濃調配物，其 中水及/或溶劑可在使用之前添加以形成移除組合物。漠 調配物可在約1:1〇至刚:！溶劑對濃縮物之範圍内稀釋其 中溶劑可為水及/或有機溶劑。 另一態樣係關於在—或多個容^中包含一或多種適於形 成本文所述移除組合物（即，第—或第二態樣）之組份的套 組。在-個實施例卜套組可在一或多個容器中包括蝕刻 劑源、至少—種界面活化劑或聚合物、視情況水、視情況 至V —種有機溶劑、視情況至少一種有機酸、視情況至少 一:氧化劑、視情況至少一種氣化物源、視情況至少一種 螯η劑、及視情況至少一種消泡劑用於如此或與稀釋劑 (J如水及/或有機溶劑）及/或消泡劑在工廠中組合。或 :，套組可包括至少一種蝕刻劑、至少一種界面活化劑或 Α物水、及視情況至少一種消泡劑用於如此或與稀釋 劑（例如，水及/或有機溶劑）及/或消泡劑在工廠中組合。 在另替代方案中，套組可包括至少一種餘刻劑、至少一 種界面活化劑、水、至少一種氣化物源、至少一種螯合 劑及視情況至少一種消泡劑用於如此或與稀釋劑（例 水及/或有機溶劑）及/或消泡劑在工廠中組合。在再一 替代中，套組可包括至少一種蝕刻劑、至少一種界面活化 劑水、至少一種氣化物源、至少一種螯合劑、及視情況 ) 種消泡劑用於如此或與稀釋劑（例如，水及/或有機 143740.doc 34- 201022148 溶劑）、消泡劑、及/或氧化劑在工廠中組合。在再一實施 例中，套組可包括至少一種蝕刻劑、至少一種界面活化劑 或聚合物及水用於如此或與稀釋劑（例如，水）及/或至少一 種氧化劑在工廠中組合。 套組之容器應化學上適於儲存及分配其中所含之組份。 舉例而σ ’套組之谷器可為NOWPak®容器（AdvancedPluronic® 17R4, Pluronic® 3 1Rl and pluronic® 25R2); alcohol alkoxylates such as Plurafac® (BASF®) (eg Plurafac® PA20); fatty alcohol alkoxylates such as Surfonic® (Huntsmen) For example, Surfonic® Pl); a blend of acid vinegar and a nonionic emulsifier such as defoamer M (Ortho Chemicals Australia Pty. 143740.doc -23-201022148) and super defoamer 225 (Varn Products) ); and its combination. Note that the antifoaming agent Μ can also act as a wetting agent, and thus it can be both an interface activator and an antifoaming agent when an antifoaming agent is used. In addition, diethylene glycol monobutyl sulphate, propylene glycol mystery, dipropylene glycol mystery (DPGME), tripropylene glycol oxime bond, dipropylene glycol dimethyl ether, dipropylene glycol, propylene glycol n-propyl ether, dipropylene glycol N-propyl ether (DPGPE), tripropylene glycol, propylene glycol, n-butyl acrylate, dipropylene glycol n-butyl ether, tripropylene glycol n-butyl ether, propylene glycol phenyl ether, and propylene glycol can be used alone or in combination with other antifoaming agents. Effectively eliminates foam. In one embodiment, the 'antifoaming agent' is selected from the group consisting of ethylene oxide/propylene oxide block copolymers, alcohol alkoxylates, fatty alcohol alkoxylates, blends of phosphates and nonionic emulsifiers, and A group of its combination. In another embodiment, the antifoaming agent is selected from the group consisting of ethylene oxide/propylene oxide block copolymers, alcohol alkoxylates, fatty alcohol alkoxylates, and combinations thereof. In a further example, the antifoaming agent is an ethylene oxide/propylene oxide block copolymer. In view of the nature of the "green" removal composition of the first aspect, the composition preferably has substantially no organic solvent including an ethyl group (e.g., #ethyl, diethyl, ethyl, etc.) and others. ΗΑρ organic solvent. For example, if an organic solvent is present, it preferably comprises a propyl group and/or a propylene glycol. It is understood that compositions comprising a solvent containing an ethyl group are also possible, as readily determined by those skilled in the art. Such compositions may be optionally combined with inactive ingredients such as, agents, pH stabilizers and the like. In a preferred embodiment, the inclusion of the additional component comprising the active ingredient as a rheological agent, a stabilizer, a passivating agent, and a dispersed "green" removal composition comprises 143740.doc • 24· 201022148 at least one A residual agent, at least one interfacial activator, water, and at least one antifoaming agent are comprised of or consist essentially of such. In still another preferred embodiment, the first aspect of the "green" removal composition comprises at least one surname, at least one interfacial activator, water, and at least one antifoaming agent, consisting or substantially And comprising the substance, wherein the antifoaming agent comprises a substance selected from the group consisting of ethylene oxide/propylene oxide block copolymer, alcohol alkoxylate, fatty alcohol alkoxylate, dish ester and Blends of nonionic emulsifiers, and combinations thereof. In another preferred embodiment, the first aspect of the "green" removal composition comprises at least one etchant, at least one interfacial activator, water, at least one antifoaming agent, at least one vapor source, and at least one The chelating agent 'constitutes or consists essentially of such. In another embodiment, the first aspect of the "green" removal composition comprises at least one etchant, at least one interfacial activator, water, at least one antifoaming agent, a seed gas source, and at least one chelating agent. And consisting of or consisting essentially of, wherein the antifoaming agent comprises a substance selected from the group consisting of ethylene oxide/propylene oxide block copolymers, alcohol alkoxylates, fatty alcohol alkanes Blends of oxylates, phosphates and nonionic emulsifiers' and combinations thereof. In still another preferred embodiment, the first aspect of the "green" removal composition comprises at least one etchant, at least one interfacial activator, water, at least one antifoaming agent, at least one vapor source, at least one oxidizing agent And at least one chelating agent' consists of or consists essentially of such. In another preferred embodiment, the first aspect of the "green" removal composition comprises at least one etchant, at least one interfacial activator, water, at least a species/foaming agent, at least one vapor source, at least one Oxidizing agent and at least 143740.doc • 25- 201022148 A chelating agent consisting of or consisting essentially of, wherein the antifoaming agent comprises a substance selected from the group consisting of: ethylene oxide/propylene oxide embedded Segment copolymers, alcohol alkoxylates, fatty alcohol alkoxylates, blends of carboxylic acid esters and nonionic emulsifiers, and combinations thereof. For example, the first aspect of the removal composition may comprise water, chlorinated money, HF, a phosphonic acid derivative integrator, an alkyl diphenyl oxide disulfonate interface activator, and an ethylene oxide/ A propylene-propylene block copolymer antifoaming agent consisting of or consisting essentially of such. Another example of the first aspect of the removal composition comprises water, gasification bonds, HF, HEDP, alkyl diphenyl oxide disulfonate interface activators, and ethylene oxide/propylene oxide block copolymerization. An antifoaming agent consisting of or consisting essentially of such an antifoaming agent. The oxidant (e.g., hydrogen peroxide) can be introduced into the composition at the manufacturer, prior to introduction of the composition into the device wafer, or at the device wafer (i.e., at the site). The first aspect of the "green" removal composition can further comprise a material residue selected from the group consisting of: post-etch residues, low-k dielectric materials, metal stack materials, high-ton dielectric materials, barrier layers Materials, ferroelectric materials, nitrides, tellurides, oxides, polymer-containing buildups, arc materials, doped regions, other materials, and combinations thereof. Preferably, the materials are dissolved and/or suspended in a "green" removal, composition and the removal of the composition still has its intended use. In a solid wipe, the -H-like "green" shift hybrid is formulated into the following concentrated examples, wherein all percentages are based on the total weight of the formulation by weight: 143740.doc -26- 201022148 Component Weight % Preferably (% by weight) optimal (% by weight) HF from about 0.01% to about 90% from about 2% to about 75% from about 5% to about 30% surfactant from about 0.01% to about 15% from about 0.1% to about 5 % about 0.5% to about 4% organic solvent 〇 to about 25% 0% to about 10% 0% to about 10% integrator 〇 to about 25% about 0.1% to about 20% about 2% to about 10% vapor Source _ 〇 to about 25% from about 0.1% to about 10% from about 1% to about 10% defoamer 〇 to about 5% from about 0.01% to about 3% from about 0.01% to about 1% water 0〇/〇 to 99 % about 5% to 90% about 10% to 70% The concentrated embodiment may include from about 1% to about 20%, more preferably from about 1% to about 15% by weight of at least one oxidizing agent, which may be pre-added and / or added at the removal site When present, the lower limit of the organic solvent and / or organic acid may be 0.01 weight ❶ / based on the total weight of the formulation. . In a particularly preferred embodiment, the weight percent of the components ranges from about 1:1 to about 10:1 pure gasification source, preferably from about 2:i to about 5, relative to the neat interfacial activator: 1 and preferably from about 3.1 to about 4:1; from about 1:1 to about 15:1 pure HF, preferably from about 3:1 to about 1 :1, and most preferably about 7 with respect to the pure interfacial activator From about 1 to about 8:i; from about 1:1 to about 10:1 pure chelating agent, preferably from about 2:1 to about 8:1, and most preferably from about 4:1 to about 5, relative to the neat interfacial activator. And a pure defoaming agent, preferably from about 0.03:1 to about 12.12:1, and most preferably from about 0.06:1 to about 100%, with respect to the pure interfacial activator. 〇.〇9:1. In various embodiments of the first aspect, the 'removal of the composition may be substantially absent from at least one of: nitric acid, sulfuric acid, decylamine (eg, hexahydropyranone and/or pyrrolidone) a supercritical fluid, an amine, and a polymer obtained by at least one polycondensation with at least one aromatic compound. In one embodiment, the first aspect of the removal composition is for recycling the microelectronic pouch structure. In other words, one 143740.doc -27-201022148 removal layer or more than one removable layer can be removed from the microelectronic device structure. In another embodiment, the first aspect of the removal composition can be used to rework the microelectronic device structure, thereby removing polymer-containing buildup on the back side and/or beveled edges of the structure. The method of removing the polymer-containing buildup from the back side and/or the beveled edge of the structure may require, but is not required to, protect the front side of the structure from exposure to the composition. Such a method can include positioning the structure on a single wafer tool that uses an inert gas (e.g., nitrogen) and/or deionized water jet to protect the front side of the wafer. Alternatively, the front side can be protected by depositing a thick photoresist layer or other protective coating polymer on the front side. In other words, if the front side of the structure includes a patterning and/or blanketing material that cannot be exposed to the first aspect of the removal composition when cleaning the back side and/or the beveled edge, the front side should be protected. In another embodiment, both the front side and the back side/bevel edge are exposed to the first aspect of the removal composition to simultaneously material from the front side (eg, low-k dielectric material, etc.) and back side/ Oblique edges (eg, polymer-containing buildup and copper-containing materials) are removed. Low-k dielectric materials removed using the removal compositions described herein include CORALTM, Black DiamondTM (hereinafter referred to as BD), derivatives of CORAL, derivatives of BD, derivatives of AURORA®, AURORA® , SiCOH, etc. As used herein, "derivatives of CORAL" and "derivatives of BD" correspond to CORAL and BD materials deposited using alternative, generally proprietary deposition methods, respectively. The use of different processing techniques will result in €:01^1^ and 80 materials that differ from CORALTM and BLACK 01, respectively. In another embodiment of the first aspect of the invention, copper ions are added to the removal composition to accelerate removal of the tungsten and tungsten containing layers from the microelectronic device structure. 143740.doc -28 · 201022148 When present, the amount of copper ions added may range from about 0.01 wt% to about 5 wt%, preferably from about 0.1 wt% to about 2 · 5 wt%, based on the total weight of the composition. %, and most preferably in the range of about 0.2 wt% to about 1 wt%. In a second aspect, another "green" or environmentally friendly removal composition is illustrated, the removal composition comprising a source of money engraving, at least one interfacial activator, water, and optionally at least one oxidizing agent, by such Composition or consist essentially of such. The components of the removal composition are present in the following ranges based on the total weight of the composition: Component % by weight of the encapsulant from about 0.01% to about 90% Interfacial activator from about 0.01% to about 15% Water from about 0.01% to about 99.98 % Oxidant 0 to about 10% The etchant and optional oxidizing agent used in the second aspect of the removal composition include those set forth above for the first aspect of the removal composition. Interfacial activators suitable for the second aspect of the removal composition include, but are not limited to, anionic interface activators such as dodecylbenzene sulfonic acid (DDBSA) or salts thereof, other linear alkyl benzene sulfonic acids (LABSA) or a salt thereof, a phosphate of an alkoxylated fatty alcohol (eg, KLEARFAC® AA270, sold by BASF Corporation); a nonionic interfacial activator such as a hydrazine ethoxylate (eg, TergitolTM 15- S-9, available from DOW), fatty alcohol alkoxylates (eg, Surfonic® (Huntsmen) (eg, Surfonic® Pl)), polyoxyethylene glycol 12-burning mystery (eg, Brij 35), and Alcohol alkoxylates (eg Plurafac® products (BASF®) (eg 'Plurafac® PA20)); polymer interface activators, eg PPG-PEG-PPG block copolymers, PEG-PPG-PEG block copolymers 143740. Doc -29- 201022148 Articles, ethylene oxide/propylene oxide block copolymers, such as piur〇nic8 (BASF®) products (eg 'piuronic® i7R2, Pluronic® 17R4, Pluronic® 31Rl and Pluronic® 25R2); Its combination. Preferably, the interfacial activator comprises an ethylene oxide/propylene oxide block copolymer. Such compositions may optionally include additional components including active ingredients as well as inactive ingredients such as rheological agents, stabilizers, passivating agents, dispersing agents, pH stabilizers, antifoaming agents, vapor sources, oxidizing agents, chelating agents. The "green" removal composition of the first aspect may further comprise a material residue selected from the group consisting of: post-etch residues, low-k dielectric materials, high-k dielectric materials, SiCN, aluminum-containing materials, barrier layer materials, ferroelectric materials, nitrides, tellurides, oxides, photoresists, polymer-containing buildups, ARC materials, doped regions, other materials, and combinations thereof. Preferably, the materials are dissolved and/or suspended in the "green" removal composition and the removal composition still has its intended use. #的性的的绿的的的物的性的性的性的性性的性性性性性性性性性性性性性性性性性性性性性性性性性性性性性性性性性性性性性性性性性性性性性性性性性性性性性性性性性性性性性性性性性性性性性性性性性性性性性性性性性性性性性性性性性性性性性性性性性性性性性性性性性性性性性性性性性性性性性性性性性性性性性性性性性性性性性性性性性性性性性性性性性性性性性性性性性性性性性性性性性性性性性性性性性性性性性性性性性性性性性性性性性性性性Organic solvent and other HAp organic solvents; nitric acid; sulfuric acid; indoleamine (for example, hexahydropyridone and/or pyrrolidone); supercritical fluid; amine; ammonium fluoride; and by at least one aldehyde and at least one A polymer obtained by polycondensation of an aromatic compound. In one embodiment, the second aspect of the "green" or environmentally friendly removal composition is formulated into the following concentrated examples, wherein the percent percentage is expressed by weight based on the total weight of the formulation: 143740.doc • 30 · 201022148 Component Weight % Preferred (% by weight) Optimum (% by weight) HF About 0.01% to about 90% About 2% to about 50% About 15% to about 25% Surfactant about 0.01% to about 15% From about 0.1% to about 10% from about 2% to about 8% water 0.01% to 99.98% from about 10% to 95% from about 65% to 85% In a particularly preferred embodiment, the second aspect of the removal composition comprises From about 17 wt% to about 23 wt% HF, from about 4 wt% to about 6 wt% interfacial activator, and from about 70 wt% to about 80 wt% water, wherein all percentages are expressed by weight based on the total weight of the formulation. When present, the amount of oxidizing agent is preferably in the range of from about 0.1% to about 10% by weight. In a particularly preferred embodiment, the weight percentages of the components range from about 1:1 to about 10:1 pure HF, preferably from about 2:1 to about 6:1, relative to the neat interfacial activator. The best is about 3:1 to about 5:1. A preferred embodiment of the second aspect of the removal composition comprises, consists of, or consists essentially of HF, PEG-PPG-PEG block copolymer and water. In another preferred embodiment, the second aspect of the removal composition comprises, consists of, or consists essentially of HF, PPG-PEG-PPG block copolymer and water. In another preferred embodiment, the second aspect of the removal composition comprises, consists of, or consists essentially of HF, a polyoxyethylene glycol dodecyl ether interface activator, and water. The oxidizing agent (e.g., hydrogen peroxide) can be introduced into the composition at the manufacturer, prior to introduction of the composition into the device wafer, or at the device wafer (i.e., at the site). In another preferred embodiment, the composition of the second aspect further comprises at least one antifoaming agent. In one embodiment, the second aspect of the removal composition is used to recover the microelectronic device structure. In other words, a removable layer 143740.doc -31 - 201022148 can be removed from the microelectronic device structure or more than one removable layer. In another embodiment, the second aspect of the removal composition can be used to rework the microelectronic device structure, thereby removing polymer-containing buildup on the back side and/or the beveled edge of the structure, such as I is described in relation to the first aspect. It should be noted that the first and second aspect of the removal composition should be substantially free of the abrasive material typically employed during the C M p treatment when the removal composition is about to come into contact with the microelectronic device. The removal composition described herein is effective to simultaneously remove at least one of the following from the surface of the microelectronic device: polymer-containing buildup, metal stack material, low dielectric layer, high-k dielectric layer, (iv) stop layer, nitride , lithium, oxide, barrier layer, photoresist, post-residue, other materials, modified regions (other than doped epitaxial Si) and/or other materials. For example, the removal of the composition can effectively remove the low-lying dielectric material from the front side of the microelectronic device while removing the polymer and other materials from the back side and/or the beveled edge of the microelectronic I, as is familiar to It is easy for the technician to determine. Thus, when performing microelectronic device fabrication operations, the removal compositions described herein can be effectively used in a single recovery or reprocessing step to remove at least one material selected from the group consisting of: for recycling from a microelectronic device structure. And/or reuse of such structures: low-k dielectric materials, high-fluid dielectric materials, etch stop layers, metal stack materials, nitrides, fragments, oxides, photoresists, barrier materials, and other materials The composition layer, polymer-containing buildup, ferroelectric material, domains (as opposed to doped epitaxial Si), and combinations thereof, are removed as described herein. Meet the recycling requirements, including (but not limited to) · G25 μπ1 particles less than 25, 0.12 μηη particles less than 5〇, or 〇〇9 μϊη particles less than 1〇〇143740.doc -32- 201022148, total thickness variation (TTV) is less than about 5 μηη (no need to remove the flattening process) 'surface metal contamination is less than lx 1〇10 atoms cm-2; and / or the thickness of the recovered substrate (no other The retention layer) is within 5% of the initial substrate thickness, preferably within 2%, and most preferably within 1%; and rework/cleaning requirements. In addition, due to the low TTV', a chemical mechanical polishing (CMP) step may not be required prior to reuse, which is a typical general recycling practice, ie 'flattening the substrate to flatten the front side of the wafer after wet removal of the material Or dorsal side. Alternatively, the parameters of the CMP step can be varied to substantially reduce the energy required, e.g., the length of the polishing time is shortened, and the like. Most preferably, after removal of material from the microelectronic device substrate, the TTV is less than 3%, more preferably less than 1% and most preferably less than 0.5%. The removal compositions described herein also meet re-use requirements, for example, to substantially remove photoresist, polymer-containing buildup, and/or electroplated copper from the outermost edges and backside of the device substrate without substantial damage. The layer to be retained. Unlike re-use compositions of the prior art (e.g., physical polishing edges, dry plasma etching, burning, etc.), at least one material to be removed from the microelectronic device structure can be removed using a wet solution. The removal compositions described herein are readily formulated by simply adding the individual ingredients and mixing them into a homogeneous state. Additionally, the removal composition can be readily formulated into a single package formulation or a plurality of formulations that are mixed at the time of use. Individual portions of the plurality of formulations may be mixed at the tool or in a storage tank upstream of the tool or both. The concentration of each component in the removal composition can vary widely, eg, more dilute or more concentrated, and it is understood that the removal of the composition may alternatively or selectively comprise any of the ingredients in accordance with the disclosure herein. .doc •33- 201022148 What constitutes, consists of, or consists essentially of. Thus, the invention relates to a composition having a small amount of water and/or solvent, or alternatively a selective formulation without water and/or solvent, wherein water and/or solvent may be added prior to use to form a removal combination. Things. The climate can be adjusted from about 1:1 to just:! The solvent is diluted within the range of the concentrate, and the solvent may be water and/or an organic solvent. Another aspect relates to a kit comprising one or more components suitable for forming a removal composition (i.e., the first or second aspect) described herein in one or more of the contents. In an embodiment, the kit may include an etchant source, at least one type of interfacial activator or polymer, optionally water, optionally V-organic solvent, optionally at least one organic acid in one or more containers. And optionally, at least one: an oxidizing agent, optionally at least one vapor source, optionally at least one chelating agent, and optionally at least one antifoaming agent for such or with a diluent (such as water and/or an organic solvent) and/or Or defoamers are combined in the factory. Or: the kit may include at least one etchant, at least one interfacial activator or hydrazine water, and optionally at least one antifoaming agent for such or with a diluent (eg, water and/or organic solvent) and/or Defoamers are combined in the factory. In a further alternative, the kit may comprise at least one residual agent, at least one interfacial activator, water, at least one vapor source, at least one chelating agent and optionally at least one antifoaming agent for such or with a diluent ( Examples of water and/or organic solvents) and/or defoamers are combined in the factory. In still another alternative, the kit can include at least one etchant, at least one interfacial activator water, at least one vapor source, at least one chelating agent, and optionally an antifoaming agent for such or with a diluent (eg, , water and/or organic 143740.doc 34- 201022148 Solvents, defoamers, and/or oxidants are combined in the factory. In still another embodiment, the kit can include at least one etchant, at least one interfacial activator or polymer, and water for combination in such a manner as or in combination with a diluent (e.g., water) and/or at least one oxidant. The container of the kit should be chemically suitable for storing and dispensing the components contained therein. For example, the σ 'set of the bar can be a NOWPak® container (Advanced

Technology Materials公司，Danbury, Conn，USA)。含有 移除組合物各組份之一或多個容器較佳包括使該一或多個 容器中之組份處於流體連通狀態以進行摻和及分配之構 件。舉例而言，參照NOWPak®容器，可將氣壓施加至該 或多個谷器之襯裏外側以排出至少一部分概襄内容物且 因此使得流體速通以進行摻和及分配。或者，可將氣壓施 加至S用可加壓之容器之頂部空間或可使用幫浦來達成流 體連通。此外，系統較佳包括將經摻和之移除組合物分配 至處理工具之分配埠。 較佳使用實質上化學惰性、無雜質、撓性及彈性聚合物 膜材料（例如，高密度聚乙烯）來製造該一或多個容器之襯 裏。合意襯裏材料經處理而無需共擠出或障壁層，且無可 不利地影響欲佈置於該襯裏中之組份的純度要求的任何顏 料、UV抑制劑、或處理劑。合意襯裏材料之列表包括含 以下物質之膜：純淨（不含添加劑）聚乙烯、純淨聚四氣乙 烯（PTFE)、聚丙烯、聚胺基曱酸酯、聚二氣亞乙烯、聚氣 乙稀、聚縮搭、聚苯乙稀、聚丙稀腈、聚丁烯等。該等概 裏材料之較佳厚度在約5密爾（0.005英吋）至約30密爾（〇 〇3〇 143740.doc -35· 201022148 英吋）之範圍内，例如厚度為20密爾（0.020英吋）。 關於套組之容器，以下專利及專利申請案之解釋内容均 以其相應整體内容引用的方式倂入本文中··美國專利第 7，188,644號，標題為「APPARATUS AND METHOD FOR MINIMIZING THE GENERATION OF PARTICLES IN ULTRAPURE LIQUIDS」：美國專利第6,698,619號，標題 為「RETURNABLE AND REUSABLE, BAG-IN-DRUM FLUID STORAGE AND DISPENSING CONTAINER SYSTEM」；國際申請案第PCT/US08/63276號，其在2008 年5月9日以John E.Q. Hughes的名字提出申請標題為 「SYSTEMS AND METHODS FOR MATERIAL BLENDING AND DISTRIBUTION」；及國際申請案第 PCT/US08/ 85826號，其在2008年12月8日以John E.Q. Hughes等人的 名字提出申請且標題為「SYSTEMS AND METHODS FOR DELIVERY OF FLUID-CONTAI NING PROCESS MATERIAL COMBINATIONS」。 除液體溶液外，本文亦預計移除組合物可調配成泡沫、 霧、緻密流體（即，超臨界或亞臨界，其中除水及/或有機 溶劑以外或代替水及/或有機溶劑，溶劑為C〇2等）。 本文所述移除組合物在單一步驟中使來自微電子裝置基 板之至少一種選自由以下組成之群之材料溶解及/或分 層：蝕刻後殘餘物、低-k介電材料、高-k介電材料、蝕刻 終止層、氮化物、矽化物、氧化物、金屬堆疊材料、鐵電 材料、障壁層、光阻劑、ARC材料、含聚合物之累積物、 143740.doc -36- 201022148 經換雜區域、及其组合(即，所有欲移除材料均可藉由使 不合格微電子裝置基板與單—組合物接觸以單次浸潰來移 除)。最佳地，可移除材料在單一步驟中溶解及/或分層， 前體條㈣在再循環㈣及/或再使用之前不需要機械抛 光如本文所疋義，「溶解」涵蓋使固體溶質（例如，欲 移除之物質）進入溶劑以形成溶液之過程。「溶解」意欲 包括欲移除物質之蝕刻、分解及/或化學拋光。溶解且有 使可隨後沉降於該基板上之特定物質的生成降至最低以及 實質上消除移除設備阻塞的優點。 有利地，在移除製程之後微電子裝置結構的剩餘層實質 上平滑且未受損壞，較佳在附加製造製程之前不需要平坦 化前側及/或背侧，即，新材料層（例如，低_k介電質、高_ k介電質、光阻劑、金屬堆疊層、蝕刻終止層等）之沈積製 程。舉例而言，若之後回收，則剩餘層僅包括微電子裝置 基板及磊晶Si層，基板較佳已準備好再循環利用/再使用而 無需昂貴且影響結構的機械拋光。應瞭解，需要時可使用 表面的機械拋光、接觸拋光或摩擦。 在另一態樣中，揭示移除方法，其中將至少一種選自由 低-k介電層、高-k介電材料、蝕刻終止層、金屬堆疊材 料、氮化物、硬化物、氧化物、鐵電材料、障壁層、光阻 劑、ARC材料、蝕刻後殘餘物、含聚合物之累積物、經摻 雜區域、及其組合組成之群的材料自其上具有該等層之微 電子裝置使用第一或第一態樣之移除組合物移除》舉例而 吕’可移除低-k介電材料同時維持下伏基板及蚀刻終止層 143740.doc •37· 201022148 (例如，SiCN、SiCO、SiC、SiON、SiGe、siGeB、 SiGeC、AlAs、InGaP、InP、inGaAs)、及金屬堆疊材料之 完整性。或者，可移除低-k介電層及金屬堆疊材料同時維 持下伏基板及/或蝕刻終止層之完整性。在另—替代中， 可移除低-k介電層、蝕刻終止層及金屬堆疊材料同時維持 下伏基板之完整性。 在再一態樣中’可使用第一或第二態樣之移除組合物來 清潔微電子裝置結構，由此移除結構之背側及/或斜邊緣 上含聚合物之累積物。在一個實施例中，自結構的背侧 及/或斜邊緣移除含聚合物之累積物的製程包括將該結構 定位於單一晶圓工具，該晶圓工具使用惰性氣體（例如， 氣氣）及/或去離子水喷射保護該結構之前側。或者，可藉 由將厚光阻劑層或其他保護塗層聚合物沈積於前側上來保 護前側。換言之，包括不想損壞的毯覆式或圖案化層的結 構前侧在清潔背側及/或斜邊緣時並未暴露於移除組人 物。在另一實施例中’將前側與背側/斜邊緣二者暴露於 移除組合物以同時將材料自前側（例如，低吨介電材料）及 背側/斜邊緣（例如，含聚合物之累積物及含鋼之材料）移 除。 被電子裝置晶圓可在廠外或廠内再加工。廠内再加工及 再循環利用具有增加總產量、降低總成本及減少診斷過程 與再加工之間的循環時間等優點。 在移除應用中’本文所述之移除組合物以任何適宜方气 與其上具有欲移除材料之不合格微電子装置接觸，例如， 143740.doc • 38 - 201022148 藉由將移除組合物噴射於裝 之裝置浸則於—定體積的移除表Λ物;:包括可移除材料 上吸收有移除組合物的另—材^物中）、使該裝置與其 耵为材枓（例如，墊或纖 劑塗施元件）接觸、使包括 ’、 ' &,入仏、 砂咏材科之裝置與再循環移 …且。 、或藉由使移除組合物與欲移除材料形成可 移除接觸的任何其他適宜途徑、方式或技術。接觸條件包 括-疋時期及足以移除可移除材料之條件4外，本文涵 蓋批量或單-晶圓處理。使用移除組合物之移除製程可包 括靜態清潔、動態清潔、或包括動態清潔、隨後靜態清潔 之相繼處理步驟以在務降知人队士士 仕移除組合物中清潔該裝置，其中相應 動態及靜態步驟在該等交替步驟之循環中交替且重複地實 施。本文所揭示任何接觸選擇條件可進_步包含超音處理 以幫助自微電子裝置移除欲移除之材料。 本文所闡述之移除組合物可與各種習用清潔工具一起使 用，其包括Verteq單一晶圓兆音波金手指（G〇idfinger)、 OnTrak Systems DDS(雙側刷洗）、LaureU旋轉喷射工具、 SEZ早日日圓噴射洗務、Applied Materials Mirra-Mesa™/Technology Materials, Danbury, Conn, USA). One or more of the containers containing the components of the removal composition preferably comprise a component that is in fluid communication with the components of the one or more containers for blending and dispensing. For example, with reference to a NOWPak® container, air pressure can be applied to the outside of the liner of the or plurality of troughs to expel at least a portion of the contents of the contents and thereby allow the fluid to pass through for blending and dispensing. Alternatively, air pressure can be applied to the headspace of the S-pressurizable container or a pump can be used to achieve fluid communication. Additionally, the system preferably includes dispensing the blended removal composition to a dispensing barrier of the processing tool. It is preferred to use a substantially chemically inert, impurity free, flexible and elastomeric polymeric film material (e.g., high density polyethylene) to make the liner of the one or more containers. The lining material is treated without the need for coextrusion or barrier layers, and without any pigment, UV inhibitor, or treatment agent that can adversely affect the purity requirements of the components to be disposed in the liner. The list of desirable lining materials includes membranes containing: pure (without additives) polyethylene, pure polytetraethylene (PTFE), polypropylene, polyamine phthalate, polydiethylene vinylene, polyethylene , polycondensation, polystyrene, polyacrylonitrile, polybutene and so on. The preferred thickness of the materials is in the range of from about 5 mils (0.005 inches) to about 30 mils (〇〇3〇143740.doc -35. 201022148 inches), for example, a thickness of 20 mils ( 0.020 inches). With regard to the container of the kit, the following patents and patent applications are hereby incorporated by reference in their entirety in their entire entire contents in U.S. Patent No. 7,188,644, entitled "APPARATUS AND METHOD FOR MINIMIZING THE GENERATION OF PARTICLES IN ULTRAPURE LIQUIDS": U.S. Patent No. 6,698,619 entitled "RETURNABLE AND REUSABLE, BAG-IN-DRUM FLUID STORAGE AND DISPENSING CONTAINER SYSTEM"; International Application No. PCT/US08/63276, which was issued on May 9, 2008 The application titled "SYSTEMS AND METHODS FOR MATERIAL BLENDING AND DISTRIBUTION" is in the name of John EQ Hughes; and International Application No. PCT/US08/85826, which was filed on December 8, 2008 under the name of John EQ Hughes et al. The application is titled "SYSTEMS AND METHODS FOR DELIVERY OF FLUID-CONTAI NING PROCESS MATERIAL COMBINATIONS". In addition to liquid solutions, it is contemplated herein that the removal composition can be formulated into a foam, mist, or dense fluid (ie, supercritical or subcritical, wherein the solvent is in addition to or in place of water and/or organic solvent, C〇2, etc.). The removal composition described herein dissolves and/or layers at least one material selected from the group consisting of microelectronic device substrates in a single step: post-etch residues, low-k dielectric materials, high-k Dielectric material, etch stop layer, nitride, germanide, oxide, metal stack material, ferroelectric material, barrier layer, photoresist, ARC material, polymer-containing accumulation, 143740.doc -36- 201022148 The swap regions, and combinations thereof (ie, all materials to be removed can be removed by contacting the failed microelectronic device substrate with the single-component for a single dipping). Preferably, the removable material is dissolved and/or layered in a single step, the precursor strip (4) does not require mechanical polishing prior to recycling (iv) and/or reuse, as defined herein, "dissolved" encompasses solid solutes The process of entering the solvent (for example, the substance to be removed) to form a solution. "Dissolution" is intended to include etching, decomposition, and/or chemical polishing of the material to be removed. It dissolves and has the advantage of minimizing the formation of specific materials that can subsequently settle on the substrate and substantially eliminating clogging of the removal device. Advantageously, the remaining layers of the microelectronic device structure are substantially smooth and undamaged after the removal process, preferably without flattening the front side and/or the back side, ie, a new material layer (eg, low) prior to the additional manufacturing process a deposition process of _k dielectric, high _k dielectric, photoresist, metal stack layer, etch stop layer, etc.). For example, if recycled later, the remaining layer includes only the microelectronic device substrate and the epitaxial Si layer, and the substrate is preferably ready for recycling/reuse without the need for expensive mechanical polishing that affects the structure. It should be understood that mechanical polishing, contact polishing or rubbing of the surface can be used as needed. In another aspect, a method of removing is disclosed, wherein at least one selected from the group consisting of a low-k dielectric layer, a high-k dielectric material, an etch stop layer, a metal stack material, a nitride, a hardened material, an oxide, an iron Materials of electrical materials, barrier layers, photoresists, ARC materials, post-etch residues, polymer-containing buildups, doped regions, and combinations thereof are used from microelectronic devices having such layers thereon The first or first aspect of the removal composition removal is exemplified by the 'removable low-k dielectric material while maintaining the underlying substrate and the etch stop layer 143740.doc • 37· 201022148 (eg, SiCN, SiCO) , SiC, SiON, SiGe, siGeB, SiGeC, AlAs, InGaP, InP, inGaAs), and the integrity of the metal stack material. Alternatively, the low-k dielectric layer and metal stack material can be removed while maintaining the integrity of the underlying substrate and/or etch stop layer. In another alternative, the low-k dielectric layer, the etch stop layer, and the metal stack material can be removed while maintaining the integrity of the underlying substrate. In still another aspect, the first or second aspect of the removal composition can be used to clean the microelectronic device structure, thereby removing polymer-containing buildup on the back side and/or beveled edges of the structure. In one embodiment, the process of removing polymer-containing buildup from the back side and/or the beveled edge of the structure includes positioning the structure to a single wafer tool that uses an inert gas (eg, gas) And/or deionized water jet protection protects the front side of the structure. Alternatively, the front side can be protected by depositing a thick photoresist layer or other protective coating polymer on the front side. In other words, the front side of the structure including the blanket or patterned layer that does not want to be damaged is not exposed to the removal group when cleaning the back side and/or the beveled edge. In another embodiment, 'the front side and the back side/beveled edges are exposed to the removal composition to simultaneously material from the front side (eg, low ton dielectric material) and back side / beveled edges (eg, polymer containing) The accumulation and the steel-containing material are removed. Wafers that are electronically processed can be reprocessed outside the factory or in the factory. In-plant reprocessing and recycling have the advantages of increased total production, lower total cost, and reduced cycle time between diagnostic and reprocessing. In the removal application, the removal composition described herein is contacted with a non-conforming microelectronic device having a material to be removed thereon in any suitable manner, for example, 143740.doc • 38 - 201022148 by removing the composition The means for spraying the device is immersed in a fixed volume of the removed material; including the other material on the removable material from which the removal composition is absorbed, and the device is made of the material (for example) , mat or fiber coating application) contact, so that including ', ' &, into the 仏, sand 咏 之 之 device and recycling ... and. Or any other suitable means, manner or technique for forming a removable contact by removing the composition from the material to be removed. This article covers batch or single-wafer processing, except for the conditions of the 疋-疋 period and the conditions 4 for removing the removable material. The removal process using the removal composition can include static cleaning, dynamic cleaning, or sequential processing steps including dynamic cleaning followed by static cleaning to clean the device in a squad squad sergeant removal composition, where the corresponding dynamics And the static step is performed alternately and repeatedly in the cycles of the alternating steps. Any of the contact selection conditions disclosed herein may include ultrasonic processing to assist in removing the material to be removed from the microelectronic device. The removal compositions described herein can be used with a variety of conventional cleaning tools, including Verteq single wafer megaphones, OnTrak Systems DDS, LaureU rotary jet tools, SEZ early yen Jet Wash, Applied Materials Mirra-MesaTM/

RefleXi〇n™/Reflexi〇n LKTM、及兆音波批量潤濕台系統。 舉例而言’可藉由添加物理組份（例如兆音波）至一步濕化 學製程以相對於基板或欲保留之層使欲移除材料之表面及 使欲移除材料之介面處機械分解來辅助如上所述移除至少 一種材料之製程。 當施加至微電子裝置製造作業時，移除組合物有效用於 自微電子裝置結構移除至少一種選自由低-k介電層、高-k 143740.doc -39- 201022148 介電材料、蝕刻終止層、金屬堆疊材料、氮化物、矽化 物、氧化物、鐵電材料、障壁層材料、光阻劑、蝕刻後殘 餘物、ARC材料、含聚合物之累積物、經摻雜區域、及其 組合組成之群之材料用於該等結構之回收、再加工再循 環利用及/或再使用。此外，應瞭解移除組合物可在化學 機械拋光製程期間使用以加速CD〇及其他低斗介電材料之 移除或CMP後製程以移除CMP後殘餘材料。 當將至少-種選自由低4介電層、高妨電材料、餘刻 終止層、金屬堆疊材料、氮化力、矽化物、氧化物、鐵電 材料、障壁層、光阻劑、蝕刻後殘餘物、ARC材料、含聚 合物之累積物、經摻雜區域、及其組合組成之群之材料自 有其之微電子裝置結構移除時，通常使移除組合物與結 構裝置在約20 C至約90。(：、較佳約20。〇至約7〇t：、最佳約 20°C至約5G°C之範圍内的溫度下接觸約3G秒至約6〇分鐘、 更佳地約75秒至約5分鐘之時間，最佳時間取決於欲移除 層之厚度。當移除蝕刻終止層時，在約2〇t至約8〇<>c之範 圍内的溫度下接觸時間可在約5分鐘至約3小時之範圍内’ 此取決於㈣終止層的厚度。該等接觸㈣及溫度係例示 性的，且在本發明之廣泛實踐内可使用有效的實質上自裝 置結構移除材料之任何其他適宜時間及溫度條件。 達成合意的移除作用之後，移除組合物可容易地自先前 其所施加之微電子裝置移除，例如，通過洗務、沖洗、乾 燥或其他移除步驟，如在本文所揭示組合物之既定最終用 途應用中所期望且有效的。舉例而言，微電子裝置可用去 143740.doc 201022148 離子水沖洗。此外，微電子裝置可利用氮氣、異丙醇或 SEZ(旋轉處理技術）進行乾燥。 在移除組合物與不合格微電子裝置結構接觸期間可使用 統計過程控制（SPC)監測並控制該等組合物。舉例而言， 可監測移除組合物浴液之SPC並控制若干輸入，其包括浴 液溫度、浴液pH、浴液主要組份之濃度、副產物之濃度及 進給化學品純度。較佳地，使用在線監測來監測移除組合 物，其中在線取樣設備可以通信方式與標準分析工具耦合 以監測浴液重量損失（其係水及/或胺損失之指示）、氟化物 濃度、H202濃度、pH等。藉由監測及/或控制該等參數中 之至少一者，可延長移除組合物浴液之壽命，此使製程效 率達到最大。SPC之目的係當進行處理時隨時間推移維持 移除組合物之若干參數的實質穩定態，如由熟悉此項技術 者所容易地確定。關於SPC，以下專利申請案之揭示内容 以其相應整體引用的方式併入本文中：2007年3月31曰提 出申請的標題為「METHOD FOR STRIPPING MATERIAL FOR WAFER RECLAMATION」之美國臨時專利申請案第 60/909,428號及2007年6月13日提出申請的標題為 「METHOD FOR STRIPPING MATERIAL FOR WAFER RECLAMATION」之美國臨時專利申請案第60/943,736 號。 令人驚奇地，本發明者發現，同一微電子裝置結構可多 次進行回收，例如，移除材料以回收基板或以回收基板及 欲保留層。舉例而言，同一基板可經處理以沈積至少一個 143740.doc -41- 201022148 材料層並隨後回收多於或等於兩次、較佳多於或等於5 次、更佳地多於或等於咐、且最佳多於或等於2〇次此 取決於方法及所沈積材料，所述回收每一次均滿足本文所 述的回收要求。回收製程較佳係單_步驟移除製程（即， 在單一步驟中使用單-組合物移除所有欲移除材料）且較 佳在進行隨後處理之前不需要回收後平坦化。換古之，如 熟悉此項技術者將瞭解，一些沈積方法及一些㈣損壞基 =其^此可能需要多種溶液及/或—些平坦化來成功回 收基板。平坦化會具有限制基板可回收之次數的影響。 _應瞭解’涵蓋至少一個步驟需要使用至少一種本文所揭 :移除組合物之多步驟移除製程。舉例而言，移除製程可 ,兩步驟製程’其中第一步驟包括使具有基板及至少一種 2移除材料之微電子裝置與本文所述之移除組合物在充分 條件（例如，如本文所揭 置移除該至少一種材料拍=觸足夠時間以自微電子裝 .^ 種材科，並將基板拋光以移除表面損壞， 其十拋光條件已為此項技術習知。 卜本發明者驚舒地發現’同一微電子裝置結構可再 (例如’㈣自微電子裝置結構移除光阻劑及a 次以上。舉你丨 士 5，同一結構可經光微影處理且隨後再加 =除錯誤定位之綠_案多於或等於2次 於或等於5次、日甚夕 舍奮 。 最佳多於或等於10次，其中該再加工不 微雷早t知壞欲保留之層。此外’本發明者驚評地發現， 如， 、、°構之身側及/或斜邊緣可容易地清潔，例 微電子裝置結構之背側及/或斜邊緣移除含聚合物 143740.doc •42· 201022148 之累積物及/或金屬而不需採用此項技術t所用之方法(例 如，物理拋光、乾電漿蝕刻、燃燒等）。 在再-態樣中，揭示包含微電子裝置之物件，其中該微 電子裝置包含使用本文所述之方法回收、再加工、再循環 利用及/或再使用之微電子裝置結構或微電子裝置基板， 該方法包含使微電子裝置結構與第一或第二態樣之移除組 合物在充分條件下接觸足夠時間以實質上移除至少一種選 自由以下μ成之群之材料：低妨電材料、高_k介電材 料钱刻終止層、金屬堆叠材料、氣化物、石夕化物、氧化 物、鐵電材料、障壁層材料、光阻劑、蝕刻後殘餘物、 ARC材料、含聚合物之累積物、經摻雜區域、及其組合。 再循環利用或再使用微電子裝置結構或微電子裝置基板可 隨後03或夕個在後續微電子裝置製造製程令沈積於其 上之層，其包括至低_k介電層、高_k介電材料餘刻終止 層、金屬堆疊材料、氮化物層、石夕化物層、氧化物層、鐵 電層、障壁層材料、經摻雜區域、及其組合中之至少一 者。 在再一態樣中’闡述一種物件’其中該物件包含再加工 微電子裝置結構或再加工微電子褒置基板及至少一選自由 以下組成之群之額外材料層：低士介電材料、高_k介電材 料、姓刻終止層、金屬堆疊材料、氮化物、石夕化物、氧化 物、鐵電材料、障壁層材料、光阻劑、ARC材料、經摻雜 區域、及其組合，其中該至少一額外材料層沈積於經再加 工後之微電子裝置結構或基板上。該物件可進一步包含定 143740.doc -43- 201022148 額外材料層之間之中 位於微電子裝置結構或基板與至少一 間層。 在再-態樣中，揭示製造包含微電子裝置之物件的方 法’其中該微電子裝置包含使用本文所述之方法回收再 加工、㈣環利用、及/或再使狀微電子裝置結構或微 電子裝置基板’該方法包含使微電子裝置結構與第一或第 二態樣之移除組合物在充分條件下接觸足夠時間以實質上 移除至少-種選自纟以下組成之群之材料：低_k介電材 料、高_k介電材料、㈣終止層、金屬堆疊材料、氮化 物、石夕化物、氡化物、鐵電材料、障壁層材料、光阻劑、 姓刻後殘餘物、ARC材料、含聚合物之累積物、經推雜區 域、及其組合。製造該物件之方法可進一步包含在後續微 電子裝置製造製程中將-或多個層沈積於再循環利用或 使用微電子裝置結構或微電子裝置基板上，其中該一或 個層包括低_k介電層、高4介電材料、蝕刻終止層、金, 堆叠材料、氮化物層、矽化物層、氧化物層、鐵電層、丨 壁層、摻雜區域、及其組合中之至少一者。 在另m本發明係關於清潔微電子裝置結構之背 侧及/或斜邊緣的方法，該方法包含：將該結構定位於使 用氮氣及/或去離子水喷射保護該結構之前侧的工具中； 及使該結構之背侧及/或斜邊緣與第一或第二態樣之移除 組合物接觸，其中該移除組合物實質上自微電子裝置基板 之背側及/或斜邊緣移除含聚合物之累積物。 處理之後，本文所述之組合物可經進一步處理以降低製 143740.doc -44· 201022148 造設施中廢水流之化學需氧量（COD)。 在另一態樣中，在使用之後且丟棄之前將消泡劑添加到 廢棄移除組合物中。 實例1 如下製備濃移除組合物：6.75 wt% NH4C1、43.6 wt% 水、30 wt% HF(49%)、15 wt% HEDP(60%)、4.5 wt% Dowfax3B2(45%)(Dowfax3B2 係作為 45 wt%溶液購得且如 此使用）及0.15 wt%消泡劑，其中該消泡劑係 Plurafac®RA20(調配物 A)、Surfonic®P 1 (調配物 B)、 Pluronic®17R2(調配物 C)、Pluronic®17R4(調配物 D)、或 Pluronic®25R2(調配物E)中之一者。每一濃組合物在使用 之前以2:1用30%過氧化氫稀釋（即，2份濃縮物對1份30% H202)。 如下製備另一序列濃移除組合物：6.75 wt% NH4C1、 47.5 wt%水、30 wt% HF(49%)、15 wt% HEDP(60%)、及 0.75 wt%消泡劑，其中該消泡劑係Plurafac®RA20(調配物 F)、Surfonic®Pl(調配物 G)、Pluronic®17R2(調配物 Η)、 Pluronic® 17R4(調配物 I)、或 Pluronic®25R2(調配物 J)中之 一者。每一濃組合物在使用之前以2:1用30%過氧化氫稀釋 (即，2份濃縮物對1份30%H2O2)。 調配物 K包括 6.75 wt% NH4C1、43.45 wt%水、30 wt°/〇 HF(49%) ' 15 wt% HEDP(60%) ' 4.5 wt% Dowfax3B2(45°/〇) 及0.6 vvt% Pluronic®25R2。調配物K在使用之前以2:1用 30%過氧化氫稀釋（即，2份濃縮物對1份30% H202)。 143740.doc -45- 201022148 調配物 L 包括 6·75 wt% NH4C1、43 wt% 水、30 wt% HF(49%) ' 15 wt% HEDP(60°/〇) ' 4.5 wt% Dowfax3B2(45%) 及0.3 wt% Pluronie®25R2。調配物L在使用之前以2:1用 30%過氧化氫稀釋（即，2份濃縮物對1份30% H202)。 於室溫（21±1°C)下將SiN、TEOS及銅之毯覆式晶圓靜止 浸潰於經H202稀釋之調配物中並測定每一者之蝕刻速 率。蝕刻速率結果顯示於下表1中： 表1 : SiN、TEOS及銅在經·Η202稀釋之調配物A-C、E、F-Η及J中之飪刻速率 調配物 溶液 ER SiN/A min·1 ERTEOS/Amin1 銅移除時間 /sec 易於沖洗？ B 澄清 69 2834 11 是 A 澄清 72 2890 10 是 C 澄清 73 3050 13 否 E 澄清 55 2595 13 否 G 澄清 62 2582 11 是 F 澄清 75 2432 10 是 Η 不澄清 60 2938 13 是 J 不澄清 101 2180 16 是 注意到，所有樣品展示類似的SiN、TEOS及銅餘刻速 率〇 對該等調配物實施起泡測試’為此在指示溫度下將調配 物在瓶子中搖晃5秒鐘並量測泡沫在溶液表面上方之高 度。結果示於表2-4中。對照沒有消泡劑且用額外的水代 替。 143740.doc •46- 201022148 表2 :覦H2〇2稀釋之調配物A_c、E、F-H及J-Κ於室a下 起泡 調配物 溶液 起泡高度/cm 0 sec 1 min 2 min 鈐照 澄清 6 6 6 B 澄清 1.75 1.5 1.25 A 澄清 1.75 1.25 1 C 澄清 1.25 1 1 E 澄清 1.5 1.3 1.25 K 不澄清 1.75 1.5 1.25 G 澄清 6 0 0 F 澄清 6 0 0 Η 不澄清 0 0 0 J 不澄清 0 0 0 表3 :經H2〇2稀釋之詷配物A、B、E及L於4〇Ί〇下起泡 調配物 溶液 起泡咼度/cm 0 sec 30 sec 1 min 2 min 1.25 3 min 0.6 B 澄清 4 3 1.75 A 澄清 4 2.5 1.5 0.75 0.5 — E 澄清 4 1.5 0.75 0.4 0.25 L 澄清 4 1.25 --_ 0.70 0.25 0.2 表4 :經私〇2稀釋之讕Β&物A、Β、Ε及L於50°C下起泡 調配物 溶液 起泡咼度/cm — 0 sec 30 sec B 澄清 5 1.8 * uiin 2 min 3 min -…"——_ A 1.0 0.6 —0.5 A 澄清 5 2.0 1.25 06 --- 0.5 b 澄清 4 1.25 0.75 04 τ--~~ —0.3 _ L 澄清 3.5 1.25 Γ 0.75 L 0.2 ' —--—-—_1 0.1 ----- ----1—--L u-z 可看出，所有消泡劑僅在2分鐘内即將組合物之起泡控 至約]cm。 亦實施銅負載試驗。舉例而言，藉由將一個usg Cu厚 度為16 kA之200 mm晶圓浸於50 g溶液中於室溫下保持2分 143740.doc • 47· 201022148 鐘可達成相當於1500個直徑300 mm且USG Cu厚度為5000 A之晶圓的銅負載。經測定，包括Plurafac®RA20、 Surfonic®P 1、及Pluronic®25R2之調配物於室溫下對相當 的1000個晶圓展示最佳負載性能，其中未在經處理銅試件 上觀察到明顯凹坑且幾乎沒有粒子。 實例2 如下製備濃移除組合物：4.5 wt°/〇 NH4C1、20 wt% HF(49%) ' 10 wt°/〇 HEDP(60°/〇) ' 3.04 wt% Dowfax3B2 (45%)、0.104 wt% Pluronic®25R2、33.4 wt% H202 (30%)、表5中所示量的額外物質，且其餘為水，其中該等 額外物質為二乙二醇單丁醚（下文中稱為BC)、二丙二醇單 丙醚（下文中稱為DPGPE)或丙二醇（下文中稱為PG)。於室 溫下實施實例1中所述的起泡高度試驗且結果展示於表5 中〇 表5:不同移除鈒合物於室滠下之起泡 額外物質的量 溶液 起泡高度/cm 15 sec 1 min 2 min 3 min 5 min 1%PG 澄清 1.75 1.5 1.25 1.0 0.5-0.75 5%PG 澄清 1.5 1.5 1.25 0.75-1 0.5 10%PG 澄清 1.75 1.5 1.25 1.0 0.5 1%BC 澄清 2.0 1.5 0.75 0.5 0 2.5%BC 稍微混濁 3.75 1.5 0.5 0 0 4.0%BC 稍微較混濁 7 <1.5 <0.5 0 0 5.0%BC 混濁 7 <0.5 0 0 0 10%BC 澄清 1.25 0 0 0 0 1%DPGPE 澄清 7 2.0 1.0 0.5 0 2.5%DPGPE 稍微混濁 7 0.5-0.75 0 0 0 3.0%DPGPE 稍微混濁 2.75 0.5-0.75 0 0 0 4.0%DPGPE 混濁 1.5 0.5 0 0 0 143740.doc -48- 201022148 5.0%DPGPE 混濁 1.25 <0.5 0 0 0 10%DPGPE 混濁，兩相 0 0 0 0 0 實例3 製備以下調配物： 調配物 Μ : 4.5 wt% NH4C1、20 wt% HF(49%)、10 wt% HEDP(60%)、3 wt% Dowfax3B2(45%)、0.1 wt%超級消泡 劑 225、33.4 wt% H2O2(30%)、29 wt%水 調配物 N : 4.5 wt% NH4C1、20 wt% HF(49%)、10 wt% HEDP(60%)、3 wt% Dowfax3B2(45%)、0.1 wt% Pluronic®31R2、 33.4 wt% H2O2(30%)、29 wt%水 讕配物 O ·· 4.5 wt% NH4C1、20 wt% HF(49%)、10 wt% HEDP(60%)、3 wt% Dowfax3B2(45%)、0.5 wt% Pluronic®25R2、 33.4 wt% H2O2(3 0%)、2 wt% 甲苯磺酸鈉、26.6 wt%水 調配物 P : 4·5 wt% NH4C1、20 wt% HF(49%)、10 wt% HEDP(60%)、3 wt〇/〇 Dowfax3B2(45%)、0.07 wt%超級消泡 劑 225、33·4 wt% H2O2(30%)、29.03 wt%水 調配物 Q : 4.5 wt% NH4C1、20 wt% HF(49°/〇)、10 wt0/〇 HEDP(60%)、3 wt% Dowfax3B2(450/〇)、0.02 wt%超級消泡 劑 225、33.4 wt% H2〇2(30%)、29.08 wt%水 調配物 R : 4.5 wt% NH4C1、20 wt% HF(49%)、10 wt% HEDP(60%)、3 wt% Dowfax3B2(45%)、0.07 wt%超級消泡 劑 225、33·4 wt% Η2〇2(30%)、0.1 wt% Pluronic®25R2、 28.93 wt%水 調配物 S : 4.5 wt% NH4C1、20 wt% HF(49%)、10 wt% HEDP(60%)、3 wt% Dowfax3B2(45%)、0.02 wt%超級消泡 143740.doc -49- 201022148 劑 225、33.4 wt% H2〇2(3〇%)、〇·1 wt% Pluronic®25R2、 28.98 wt%水 謂》物 T : 4.5 wt。/。NH4C1、20 wt% HF(49%)、10 wt0/〇 HEDP(60%)、3 wt% Dowfax3B2(45%)、0.3 wt% Pluronic®31R2、 33.4 wt% H2〇2(3〇%)、2.5 wt% PG、26.3 wt%水 調配物 U : 4.5 wt% NH4C1、20 wt% HF(49%)、10 wt% HEDP(60%)、3 wt% Dowfax3B2(45%)、0.3 wt% Pluronic®31R2、 33.4 wt% H2〇2(3〇%)、5 wt%PG、23.8 wt%水 於室溫下實施實例1中所述的起泡高度試驗且結果展示 於表6中。 表6:不同移除组合物於室溫下之起泡 調配物 溶液狀況 起泡高度/cm 15 sec 1 min 2 min 3 min 5 min 10 min Μ 稍微混濁，瓶壁上有油 2 0.5 0 0 0 0 Ν 稍微混濁，瓶壁上有少 許油 3 1.25- 1.0 0.5 0 0 〇 稍微混濁，瓶壁上有少 許油 1 0.25 0 0 0 Ρ 澄清 4 1 0.5 0 0 Q 澄清 1.25 0.25- 0.5 0 0 R 稍微混濁 1.5 1.25 1.25 1.25 1 1 S 稍微混濁 1.25 1 1 0 0.75 Τ 稍微混濁 1.25 1 1 0.75 0.5 U 稍微混濁 1.5 1.25 1 0.75 0.5 0 實例4 製備實例1中所述的調配物E。在使用之前將其以2·· 1用 30%過氧化氫稀釋（即，2份濃縮物對1份30% H202)。使含 有Ηζ〇2之調配物裝載銅離子，如表7中所指示。將鎢晶圓 143740.doc 50- 201022148 (在約80 nm厚之障壁層上約5600 A厚）於21 °C下於組合物中 浸潰5或10分鐘，去除並用DI水沖洗並獲得晶圓之電子顯 微照片。RefleXi〇nTM/Reflexi〇n LKTM, and megaphone batch wetting station system. For example, 'by adding physical components (such as megasonic waves) to a one-step wet chemical process to assist in mechanically decomposing the surface of the material to be removed and the interface of the material to be removed relative to the substrate or the layer to be retained The process of removing at least one material as described above. The removal composition is effective for removing at least one dielectric material selected from the low-k dielectric layer, high-k 143740.doc-39-201022148, etched from the microelectronic device structure when applied to the microelectronic device fabrication operation. Termination layer, metal stack material, nitride, germanide, oxide, ferroelectric material, barrier layer material, photoresist, post-etch residue, ARC material, polymer-containing buildup, doped region, and The materials of the combined group are used for the recovery, reprocessing, recycling and/or reuse of such structures. In addition, it is understood that the removal composition can be used during the chemical mechanical polishing process to accelerate the removal of CD 〇 and other low-pitched dielectric materials or post-CMP processes to remove residual material after CMP. When at least one selected from the group consisting of a low dielectric layer, a high-lying electrical material, a residual termination layer, a metal stacking material, a nitriding force, a telluride, an oxide, a ferroelectric material, a barrier layer, a photoresist, and an etch The material of the residue, ARC material, polymer-containing buildup, doped regions, and combinations thereof, when removed from the structure of the microelectronic device, typically results in a removal composition and structural device at about 20 C to about 90. (:, preferably about 20. 〇 to about 7 〇 t: preferably at a temperature in the range of about 20 ° C to about 5 ° C for about 3 G seconds to about 6 minutes, more preferably about 75 seconds. For a period of about 5 minutes, the optimum time depends on the thickness of the layer to be removed. When the etch stop layer is removed, the contact time can be at a temperature in the range of about 2 〇t to about 8 〇 <> Within a range of from about 5 minutes to about 3 hours' depending on the thickness of the (iv) termination layer. The contacts (iv) and temperature are exemplary and can be removed using an effective substantially self-contained structure within the broad practice of the invention. Any other suitable time and temperature conditions for the material. After a desirable removal is achieved, the removal composition can be easily removed from the microelectronic device to which it was previously applied, for example, by washing, rinsing, drying, or other removal. The steps are as desired and effective in the intended end use applications of the compositions disclosed herein. For example, the microelectronic device can be rinsed with 143740.doc 201022148 ionized water. In addition, the microelectronic device can utilize nitrogen, isopropanol Or drying with SEZ (Rotary Processing Technology) The composition can be monitored and controlled using statistical process control (SPC) during removal of the composition from contact with the failed microelectronic device structure. For example, the SPC removing the composition bath can be monitored and several inputs can be controlled, It includes bath temperature, bath pH, concentration of the main component of the bath, concentration of by-products, and purity of the feed chemical. Preferably, online monitoring is used to monitor the removal composition, wherein the on-line sampling device can communicate Coupled with a standard analytical tool to monitor bath weight loss (which is indicative of water and/or amine loss), fluoride concentration, H202 concentration, pH, etc. By monitoring and/or controlling at least one of the parameters, The life of the removal of the composition bath can be extended, which maximizes process efficiency. The purpose of the SPC is to maintain a substantially stable state of removal of several parameters of the composition over time as it is processed, as is known to those skilled in the art. It is easy to determine. With regard to SPC, the disclosure of the following patent application is hereby incorporated by reference in its entirety in its entirety: U.S. Provisional Patent Application Serial No. 60/909,428, filed on Jun. Surprisingly, the inventors have discovered that the same microelectronic device structure can be recycled multiple times, for example, removing material to recover a substrate or to recover a substrate and to retain a layer. For example, the same substrate can be processed to Depositing at least one 143740.doc -41 - 201022148 material layer and subsequently recovering more than or equal to two, preferably more than or equal to 5, more preferably more than or equal to 咐, and optimally more than or equal to 2 〇 Depending on the method and the materials deposited, the recovery meets the recycling requirements described herein each time. The recycling process is preferably a one-step removal process (i.e., using a single-composition to remove all of the material to be removed in a single step) and preferably does not require post-recovery planarization prior to subsequent processing. In the past, those skilled in the art will appreciate that some deposition methods and some (4) damage bases may require multiple solutions and/or flattening to successfully recover the substrate. Flattening can have the effect of limiting the number of times the substrate can be recycled. _ should be understood to cover at least one step requiring the use of at least one of the multiple removal processes described herein for removing the composition. For example, the removal process can be a two-step process wherein the first step includes subjecting the microelectronic device having the substrate and the at least one removal material to the removal composition described herein under sufficient conditions (eg, as herein) Removing and removing the at least one material 拍 = touching for a sufficient time to self-microelectronics, and polishing the substrate to remove surface damage, the ten polishing conditions are known in the art. Suddenly found that 'the same microelectronic device structure can be re- (for example, '(4) remove the photoresist from the microelectronic device structure and more than a. As you gentleman 5, the same structure can be processed by photolithography and then added = In addition to the wrong positioning of the green _ case more than or equal to 2 times at or equal to 5 times, the day is very happy. The best is more than or equal to 10 times, wherein the re-processing is not a slight thunder and early to know the layer of bad desire to retain. Furthermore, the inventors have found that, for example, the side of the body and/or the beveled edge can be easily cleaned, such as the back side and/or the beveled edge of the microelectronic device structure to remove polymer-containing 143740.doc • 42· 201022148 Accumulations and / or metals without the need for mining The method used in the art t (eg, physical polishing, dry plasma etching, combustion, etc.). In a re-state, an article comprising a microelectronic device is disclosed, wherein the microelectronic device comprises recycling using the methods described herein. , reprocessing, recycling, and/or reuse of a microelectronic device structure or microelectronic device substrate, the method comprising contacting the microelectronic device structure with the first or second aspect of the removal composition under sufficient conditions Time to substantially remove at least one material selected from the group consisting of: a low-lying electrical material, a high-k dielectric material, a stop layer, a metal stack material, a vapor, a lithium, an oxide, a ferroelectric Materials, barrier layer materials, photoresists, post-etch residues, ARC materials, polymer-containing buildups, doped regions, and combinations thereof. Recycling or reuse of microelectronic device structures or microelectronic device substrates Subsequently 03 or a subsequent layer deposited on the subsequent microelectronic device manufacturing process, including a low-k dielectric layer, a high-k dielectric material remnant stop layer, a metal stack material, nitrogen At least one of a layer of material, a layer of lithiation, an oxide layer, a ferroelectric layer, a barrier layer material, a doped region, and combinations thereof. In another aspect, 'an object is described' wherein the object contains Processing the microelectronic device structure or reworking the microelectronic mounting substrate and at least one additional material layer selected from the group consisting of: a low dielectric material, a high-k dielectric material, a surname layer, a metal stack material, nitrogen a compound, a lithiate, an oxide, a ferroelectric material, a barrier layer material, a photoresist, an ARC material, a doped region, and combinations thereof, wherein the at least one additional material layer is deposited on the reprocessed microelectronic device The structure or substrate. The article may further comprise a layer 143740.doc-43-201022148 between the additional material layers located in the microelectronic device structure or substrate and at least one layer. In a re-state, a method of fabricating an article comprising a microelectronic device is disclosed, wherein the microelectronic device comprises recycling, reprocessing, (d) ring utilization, and/or re-forming the microelectronic device structure or microfabric using the methods described herein. Electronic Device Substrate 'The method comprises contacting the microelectronic device structure with the first or second aspect of the removal composition under sufficient conditions for a time sufficient to substantially remove at least one material selected from the group consisting of: Low-k dielectric material, high-k dielectric material, (iv) termination layer, metal stack material, nitride, alexandry, telluride, ferroelectric material, barrier layer material, photoresist, surname residue, ARC materials, polymer-containing buildups, intertwined regions, and combinations thereof. The method of making the article can further comprise depositing - or layers in a subsequent microelectronic device fabrication process on recycling or using a microelectronic device structure or a microelectronic device substrate, wherein the one or more layers comprise a low _k At least one of a dielectric layer, a high dielectric material, an etch stop layer, a gold, a stack material, a nitride layer, a germanide layer, an oxide layer, a ferroelectric layer, a germanium layer, a doped region, and combinations thereof By. In another aspect, the invention relates to a method of cleaning a back side and/or a beveled edge of a microelectronic device structure, the method comprising: positioning the structure in a tool that protects the front side of the structure using nitrogen and/or deionized water spray; And contacting the back side and/or the beveled edge of the structure with the first or second aspect of the removal composition, wherein the removal composition is substantially removed from the back side and/or the beveled edge of the microelectronic device substrate A polymer-containing buildup. After treatment, the compositions described herein can be further processed to reduce the chemical oxygen demand (COD) of the wastewater stream in the 143740.doc-44. 201022148 facility. In another aspect, the antifoaming agent is added to the waste removal composition after use and prior to disposal. Example 1 A concentrated removal composition was prepared as follows: 6.75 wt% NH4C1, 43.6 wt% water, 30 wt% HF (49%), 15 wt% HEDP (60%), 4.5 wt% Dowfax 3B2 (45%) (Dowfax 3B2 system as 45 wt% solution purchased and used as such) and 0.15 wt% defoamer, wherein the defoamer is Plurafac® RA20 (formulation A), Surfonic® P 1 (formulation B), Pluronic® 17R2 (formulation C) One of Pluronic® 17R4 (Formulation D) or Pluronic® 25R2 (Formulation E). Each concentrated composition was diluted with 2:1 with 30% hydrogen peroxide (i.e., 2 parts concentrate to 1 part 30% H202) before use. Another sequence of concentrated removal compositions was prepared as follows: 6.75 wt% NH4C1, 47.5 wt% water, 30 wt% HF (49%), 15 wt% HEDP (60%), and 0.75 wt% defoamer, wherein The foaming agent is in Plurafac® RA20 (Formulation F), Surfonic® Pl (Formulation G), Pluronic® 17R2 (Formulation Η), Pluronic® 17R4 (Formulation I), or Pluronic® 25R2 (Formulation J) One. Each concentrated composition was diluted with 30% hydrogen peroxide at 2:1 prior to use (i.e., 2 parts concentrate to 1 part 30% H2O2). Formulation K includes 6.75 wt% NH4C1, 43.45 wt% water, 30 wt/〇HF (49%) '15 wt% HEDP (60%) '4.5 wt% Dowfax3B2 (45°/〇) and 0.6 vvt% Pluronic® 25R2. Formulation K was diluted 2:1 with 30% hydrogen peroxide prior to use (i.e., 2 parts concentrate to 1 part 30% H202). 143740.doc -45- 201022148 Formulation L includes 6.75 wt% NH4C1, 43 wt% water, 30 wt% HF (49%) '15 wt% HEDP (60°/〇) ' 4.5 wt% Dowfax3B2 (45% ) and 0.3 wt% Pluronie® 25R2. Formulation L was diluted 2:1 with 30% hydrogen peroxide prior to use (i.e., 2 parts concentrate to 1 part 30% H202). SiN, TEOS, and copper blanket wafers were statically impregnated in H202 diluted formulations at room temperature (21 ± 1 °C) and the etch rate was determined for each. The etch rate results are shown in Table 1 below: Table 1: Preparation of SiN, TEOS, and copper in the formulations of AC, E, F-Η, and J diluted in Η202, ER SiN/A min·1 ERTEOS/Amin1 Copper removal time / sec Easy to rinse? B Clarification 69 2834 11 Yes A Clarification 72 2890 10 Yes C Clarification 73 3050 13 No E Clarification 55 2595 13 No G Clarification 62 2582 11 Yes F Clarification 75 2432 10 Yes Η No clarification 60 2938 13 Yes J No clarification 101 2180 16 Yes Note that all samples exhibited similar SiN, TEOS, and copper re-rates. The foaming test was performed on the formulations. For this purpose, the formulation was shaken in the bottle for 5 seconds at the indicated temperature and the foam was measured on the surface of the solution. The height above. The results are shown in Tables 2-4. The control did not have an antifoaming agent and was replaced with additional water. 143740.doc •46- 201022148 Table 2: Formulations of 觎H2〇2 diluted formulations A_c, E, FH and J-Κ under chamber a Foaming solution solution Foaming height / cm 0 sec 1 min 2 min Reference clarification 6 6 6 B Clarification 1.75 1.5 1.25 A Clarification 1.75 1.25 1 C Clarification 1.25 1 1 E Clarification 1.5 1.3 1.25 K Not Clarified 1.75 1.5 1.25 G Clarification 6 0 0 F Clarification 6 0 0 Η Not Clarified 0 0 0 J Not Clarified 0 0 0 Table 3: 詷 詷 A, B, E and L diluted with H2 〇 2 at 4 起 foaming formulation solution foaming temperature / cm 0 sec 30 sec 1 min 2 min 1.25 3 min 0.6 B Clarification 4 3 1.75 A Clarification 4 2.5 1.5 0.75 0.5 — E Clarification 4 1.5 0.75 0.4 0.25 L Clarification 4 1.25 --_ 0.70 0.25 0.2 Table 4: 谰Β & A, Β, Ε and L diluted by 〇 2 Foaming solution solution foaming temperature at 50 ° C / cm — 0 sec 30 sec B Clarification 5 1.8 * uiin 2 min 3 min -..."——_ A 1.0 0.6 —0.5 A Clarification 5 2.0 1.25 06 -- - 0.5 b Clarification 4 1.25 0.75 04 τ--~~ —0.3 _ L Clarification 3.5 1.25 Γ 0.75 L 0.2 ' —-----_1 0.1 ----- ----1—--L uz Out, all defoamers Within 2 minutes of coming composition was controlled to about bubbler] cm. A copper load test was also carried out. For example, by immersing a 200 mm wafer with a thickness of 16 kA in a 50 g solution in a 50 g solution at room temperature for 2 minutes 143740.doc • 47· 201022148 clocks can be equivalent to 1500 diameters of 300 mm and The copper load of the USG Cu wafer with a thickness of 5000 A. Formulations including Plurafac® RA20, Surfonic® P 1 , and Pluronic® 25R2 were tested to demonstrate optimal load performance on comparable 1000 wafers at room temperature, with no apparent obscuration observed on the treated copper coupons. Pit and almost no particles. Example 2 A concentrated removal composition was prepared as follows: 4.5 wt ° / 〇 NH 4 C1 , 20 wt % HF (49%) ' 10 wt ° / 〇 HEDP (60 ° / 〇) ' 3.04 wt% Dowfax 3B2 (45%), 0.104 wt % Pluronic® 25R2, 33.4 wt% H202 (30%), additional substances in the amounts shown in Table 5, and the balance being water, wherein the additional substances are diethylene glycol monobutyl ether (hereinafter referred to as BC), Dipropylene glycol monopropyl ether (hereinafter referred to as DPGPE) or propylene glycol (hereinafter referred to as PG). The foam height test described in Example 1 was carried out at room temperature and the results are shown in Table 5. Table 5: Different amounts of foaming extra substances removed under the chamber at room temperature Foaming height/cm 15 Sec 1 min 2 min 3 min 5 min 1%PG Clarification 1.75 1.5 1.25 1.0 0.5-0.75 5% PG Clarification 1.5 1.5 1.25 0.75-1 0.5 10% PG Clarification 1.75 1.5 1.25 1.0 0.5 1% BC Clarification 2.0 1.5 0.75 0.5 0 2.5 %BC slightly turbid 3.75 1.5 0.5 0 0 4.0% BC slightly turbid 7 <1.5 <0.5 0 0 5.0% BC turbidity 7 <0.5 0 0 0 10% BC Clarification 1.25 0 0 0 0 1%DPGPE Clarification 7 2.0 1.0 0.5 0 2.5% DPGPE slightly turbid 7 0.5-0.75 0 0 0 3.0%DPGPE slightly turbid 2.75 0.5-0.75 0 0 0 4.0%DPGPE turbidity 1.5 0.5 0 0 0 143740.doc -48- 201022148 5.0%DPGPE turbidity 1.25 < 0.5 0 0 0 10%DPGPE turbidity, two phases 0 0 0 0 0 Example 3 The following formulations were prepared: Formulation Μ : 4.5 wt% NH4C1, 20 wt% HF (49%), 10 wt% HEDP (60%), 3 wt% Dowfax 3B2 (45%), 0.1 wt% super defoamer 225, 33.4 wt% H2O2 (30%), 29 wt% water formulation N: 4.5 wt% NH4C1, 20 wt% HF (49%), 10 Wt% HEDP (60%), 3 wt% Do wfax3B2 (45%), 0.1 wt% Pluronic® 31R2, 33.4 wt% H2O2 (30%), 29 wt% hydroquinone formulation O ·· 4.5 wt% NH4C1, 20 wt% HF (49%), 10 wt% HEDP (60%), 3 wt% Dowfax3B2 (45%), 0.5 wt% Pluronic® 25R2, 33.4 wt% H2O2 (30%), 2 wt% sodium toluenesulfonate, 26.6 wt% water formulation P: 4·5 Wt% NH4C1, 20 wt% HF (49%), 10 wt% HEDP (60%), 3 wt〇/〇Dowfax3B2 (45%), 0.07 wt% super defoamer 225, 33.4 wt% H2O2 (30 %), 29.03 wt% water formulation Q: 4.5 wt% NH4C1, 20 wt% HF (49°/〇), 10 wt0/〇 HEDP (60%), 3 wt% Dowfax3B2 (450/〇), 0.02 wt% Super defoamer 225, 33.4 wt% H2〇2 (30%), 29.08 wt% water formulation R: 4.5 wt% NH4C1, 20 wt% HF (49%), 10 wt% HEDP (60%), 3 wt % Dowfax3B2 (45%), 0.07 wt% super defoamer 225, 33.4 wt% Η2〇2 (30%), 0.1 wt% Pluronic® 25R2, 28.93 wt% water formulation S: 4.5 wt% NH4C1, 20 Wt% HF (49%), 10 wt% HEDP (60%), 3 wt% Dowfax3B2 (45%), 0.02 wt% super defoaming 143740.doc -49- 201022148 agent 225, 33.4 wt% H2〇2 (3 〇%), 〇·1 wt% Pluronic® 25R2, 28.98 wt% water is said to be T: 4.5 wt. /. NH4C1, 20 wt% HF (49%), 10 wt0/〇 HEDP (60%), 3 wt% Dowfax3B2 (45%), 0.3 wt% Pluronic® 31R2, 33.4 wt% H2〇2 (3〇%), 2.5 Wt% PG, 26.3 wt% water formulation U: 4.5 wt% NH4C1, 20 wt% HF (49%), 10 wt% HEDP (60%), 3 wt% Dowfax 3B2 (45%), 0.3 wt% Pluronic® 31R2 33.4 wt% H2〇2 (3〇%), 5 wt% PG, 23.8 wt% water The foaming height test described in Example 1 was carried out at room temperature and the results are shown in Table 6. Table 6: Foaming solution solution conditions at different room temperature at different room temperature Foaming height / cm 15 sec 1 min 2 min 3 min 5 min 10 min Μ slightly turbid, oil on the bottle wall 2 0.5 0 0 0 0 稍微 slightly turbid, a little oil on the bottle wall 3 1.25- 1.0 0.5 0 0 〇 slightly turbid, a little oil on the bottle wall 1 0.25 0 0 0 Ρ clarification 4 1 0.5 0 0 Q clarification 1.25 0.25- 0.5 0 0 R slightly Turbidity 1.5 1.25 1.25 1.25 1 1 S slightly turbid 1.25 1 1 0 0.75 稍微 slightly turbid 1.25 1 1 0.75 0.5 U slightly turbid 1.5 1.25 1 0.75 0.5 0 Example 4 Formulation E described in Example 1 was prepared. It was diluted with 2% 1% with 30% hydrogen peroxide before use (i.e., 2 parts concentrate to 1 part 30% H202). The formulation containing ruthenium 2 was loaded with copper ions as indicated in Table 7. Tungsten wafer 143740.doc 50- 201022148 (about 5600 A thick on a barrier layer of about 80 nm thick) was dipped in the composition at 21 ° C for 5 or 10 minutes, removed and rinsed with DI water to obtain a wafer. Electron micrograph.

表7 :調配物AB-AETable 7: Formulation AB-AE

調配物 處理時間及溫度 化學品 E 27〇C * 10 min 僅調配物E AB 21°C 5 5 min 含有約2.4 wt%來自晶圓之Cu離子的E卞 AC 21°C · 10 min 含有約2.4 wt%來自Cu金屬之Cu離子的E AD 21°C > 10 min 含有约0.4 wt%來自Cu金屬之Cu離子的E AE 21〇C，l〇min 含有約0.09 wt%來自Cu金屬之Cu離子的E T Cu離子係藉由將1個200 mm Cu晶圓（16.5 kA)溶於50 g調 配物E中獲得 參照圖1 A-1E中之電子顯微照片（其分別對應於與在調配 物E及AB-AE中浸潰相關之結果），可以看出以低至0.4 wt%(以組合物之總重量計）之濃度存在的銅離子於室溫下 僅在10分鐘内即可完全移除鎢層及下伏障壁層。 實例5 製備以下調配物： 調配物BA : 40 wt% HF(49%)、0.1 wt% Brij 35、59.9 wt%水 調配物 BB : 40 wt% HF(49%)、0.5 wt% Brij 35、59.5 wt%水 調》物 BC : 40 wt°/〇 HF(49%)、1 wt% Brij 35、59 wt°/〇水 調配物BD : 40 wt°/〇 HF(49%)、0.1 wt% PEG-PPG-PEG嵌段 共聚物、59.9 wt%水 調配物 BE : 40 wt。/。HF(49%)、0.5 wt% PEG-PPG-PEG嵌段 143740.doc -51- 201022148 共聚物、59.5 wt%水 調配物 BF: 40 wt% HF(49%)、1 wt% PEG-PPG-PEG嵌段 共聚物、59 wt%水 調配物 BG : 40 wt% HF(49%)、0.1 wt% PPG-PEG-PPG 嵌段 共聚物、59.9 wt%水 調配物BH : 40 wt% HF(49%).、0.5 wt% PPG-PEG-PPG嵌段 共聚物、59.5 wt%水 調配物 BI : 40 wt% HF(49%)、1 wt% PPG-PEG-PPG 嵌段共 聚物、59 wt%水 調配物 BJ : 40 wt% HF(49%)、0.1 wt% DDBSA、59.9 wt% 水 調配物BK : 40 wt% HF(49%)、0.5 wt% DDBSA、59.5 wt% 水 調配物 BL : 40 wt% HF(49%)、1 wt% DDBSA、59 wt%水 調配物 BM : 40 wt% HF(49%)、0.1 wt% Biosoft S-100、 59.9 wt%水 調配物 BN : 40 wt% HF(49%)、0.5 wt% Biosoft S-100、 59.5 wt%水 調配物 BO : 40 wt% HF(49%)、1 wt% Biosoft S-100、59 wt%水 於70°C下將k值多於或等於2.7之黑金剛石的F-20試件 (Advantiv，5000 A)於調配物BA-BO中浸潰20分鐘。對於每 一樣品針對每一試件實施兩次重複測試。在20分鐘結束 時，人工自單元吸取化學品並置於離心管中進行目視分 143740.doc -52- 201022148 . 析。將試件及溶液以（在適當情況下）完整膜保留、明顯殘 留、略有殘留（幾乎不可見）或全部清除進行分級。使用黑 金剛石k>2.7之結果提供於表8中。 表8 :黑金剛石試件（k>2.7)於調配物BA-BO中浸溃之結果 調配物 結果(試件） 結果(溶液） BA 全部清除 完全澄清 BA 全部清除 完全澄清 BB 略有殘留 完全澄清 BB 全部清除 完全澄清 BC 全部清除 完全澄清 BC 全部清除 完全澄清 BD 全部清除 完全澄清 BD 全部清除 完全澄清 BE 全部清除 完全澄清 BE 全部清除 完全澄清 BF 全部清除 完全澄清 BF 全部清除 完全澄清 BG 略有殘留 完全澄清 BG 略有殘留 完全澄清 BH 全部清除 完全澄清 BH 略有殘留 完全澄清 BI 略有殘留 完全澄清 BI 略有殘留 完全澄清 BJ 全部清除 褐色殘餘物 BJ 全部清除 褐色殘餘物 BK 全部清除 褐色殘餘物 BK 全部清除 褐色殘餘物 BL 全部清除 褐色殘餘物 BL 全部清除 褐色殘餘物 BM 全部清除 漂浮殘餘物 BM 全部清除 溶液中有殘留 BN 全部清除 雙色相 BN 全部清除 雙色相 BO 全部清除 雙色相 BO 全部清除 雙色相 可以看出，包括Brij 35或PEG-PPG-PEG嵌段共聚物之組 143740.doc -53- 201022148 合物成功自試件移除所有黑金剛石且所得溶液無殘餘物。 此外，包括DDBSA及Biosoft S-100之組合物成功自試件移 除所有黑金剛石。 應注意，當用k值為2.4之黑金剛石試件測試調配物時’ 包括PEG-PPG-PEG或DDBSA之調配物有效自試件移除所 有黑金剛石且所得組合物無殘餘物。 實例6 製備以下調配物CA及CB用於使用COD燃燒技術進行 COD測試。特定而言，該測試測定使水樣品中經還原之化 合物氧化所需氧的數量。將氧化劑、觸媒及樣品於1 50°c 下處理2小時： 調配物 CA: 40 wt% HF(49%)、3 wt% PEG-PPG-PEG嵌段 共聚物、57 wt%水 調配物 CB : 40 wt% HF(49%)、5 wt% PEG-PPG-PEG嵌段 共聚物、55 wt%水 調配物CA及CB以25 0:1、500:1及1〇〇〇:1用水稀釋並測定 COD值（以mg/L表示）。結果提供於下表9中。 表9:經稀釋調》物CA及CB之COD值 調配物 稀釋 COD平均值(mg/L) CA 250:1 307.4 CA 250:1 296.0 CA 500:1 103.2 CA 500:1 148.8 CA 500:1 104.3 CA 1000:1 _ 65.5 CA 1000:1 75.2 143740.doc •54- 201022148 CB 250:1 ----- CB 250:1 ____ 315.2 CB 500:1 224 0 CB 500:1 ——255 8 CB 1000:1 —~__ 118.6 CB 1000:1 L——_ 101.3 為顯示兆音波在移除材料方, 刊竹万面之有效性，如下製備調配 物DA : 1.5 wt% 調配物DA: 20.1 wt%HF、57.5 wt% 丁基卡必醇 環 丁颯、10 wt% Η202、10·9 wt%水 於35。(：下將P-SiCOH浸潰於調配物DA中並經受死音波處 理1〇分鐘。對於k值為3·〇、2.7'2.4及2々p.Sic〇H，所 有ρ-SiCOH均被剝除❿無任何剩餘殘餘物。❿且，剩餘表 面平滑。同樣，於饥下使用死音波調配物da僅在_ 鐘中内即自晶圓表面移除黑金剛石π。 因此’儘管本文已參照本發明之具體態樣、特徵及例示 性實施例闡述本發明，但應理解，本發明之用途並不因此 受限，而是可擴展至並涵蓋諸多其他態樣、特徵、及實施 例。因此，意文料之巾料利_相應地理解為 廣泛包括屬於其精神及範圍内之所有該等態樣、特徵、及 實施例。 ^ 【圖式簡單說明】 圖1Α係鎢晶圓在調配物ε中浸潰後之電子顯微照片. 圖1Β係鶴晶圓在調配物ΑΒ中浸潰德之雷之Β <电千顯微照片； 圖1C係鶴晶圓在調配物AC中浸潰德之雷 电千顯微照片； 143740.doc -55 201022148 圖ID係鎢晶圓在調配物AD中浸潰後之電子顯微照 片；及 圖1E係鎢晶圓在調配物AE中浸潰後之電子顯微照片。 143740.doc •56-Formulation treatment time and temperature Chemicals E 27〇C * 10 min Formulation only E AB 21 ° C 5 5 min E卞AC 21 °C containing approximately 2.4 wt% Cu ions from the wafer · 10 min Contains approximately 2.4 Wt% E AD from Cu metal of Cu metal 21 °C > 10 min E AE 21〇C containing about 0.4 wt% Cu ion from Cu metal, l〇min contains about 0.09 wt% Cu ion from Cu metal The ET Cu ion was obtained by dissolving a 200 mm Cu wafer (16.5 kA) in 50 g of Formulation E to obtain an electron micrograph in Figure 1 A-1E (which corresponds to the formulation E, respectively). And the results associated with impregnation in AB-AE), it can be seen that copper ions present in concentrations as low as 0.4 wt% (based on the total weight of the composition) can be completely removed in only 10 minutes at room temperature. Tungsten layer and underlying barrier layer. Example 5 The following formulations were prepared: Formulation BA: 40 wt% HF (49%), 0.1 wt% Brij 35, 59.9 wt% water formulation BB: 40 wt% HF (49%), 0.5 wt% Brij 35, 59.5 Wt% water-regulating substance BC: 40 wt°/〇HF (49%), 1 wt% Brij 35, 59 wt°/hydrophobic formulation BD: 40 wt°/〇HF (49%), 0.1 wt% PEG - PPG-PEG block copolymer, 59.9 wt% water formulation BE: 40 wt. /. HF (49%), 0.5 wt% PEG-PPG-PEG block 143740.doc -51- 201022148 Copolymer, 59.5 wt% water formulation BF: 40 wt% HF (49%), 1 wt% PEG-PPG- PEG block copolymer, 59 wt% water formulation BG: 40 wt% HF (49%), 0.1 wt% PPG-PEG-PPG block copolymer, 59.9 wt% water formulation BH: 40 wt% HF (49 %)., 0.5 wt% PPG-PEG-PPG block copolymer, 59.5 wt% water formulation BI: 40 wt% HF (49%), 1 wt% PPG-PEG-PPG block copolymer, 59 wt% Water Formulation BJ: 40 wt% HF (49%), 0.1 wt% DDBSA, 59.9 wt% Water Formulation BK: 40 wt% HF (49%), 0.5 wt% DDBSA, 59.5 wt% Water Formulation BL: 40 Wt% HF (49%), 1 wt% DDBSA, 59 wt% water formulation BM: 40 wt% HF (49%), 0.1 wt% Biosoft S-100, 59.9 wt% water formulation BN: 40 wt% HF (49%), 0.5 wt% Biosoft S-100, 59.5 wt% water formulation BO: 40 wt% HF (49%), 1 wt% Biosoft S-100, 59 wt% water at 70 ° C k value A F-20 test piece (Advantiv, 5000 A) of more than or equal to 2.7 black diamond was immersed in the formulation BA-BO for 20 minutes. Two replicate tests were performed for each test piece for each sample. At the end of 20 minutes, the chemical was manually drawn from the unit and placed in a centrifuge tube for visual inspection. 143740.doc -52- 201022148 . The test piece and solution are classified as (where appropriate) intact film retained, markedly left, slightly residual (almost invisible) or completely removed. The results using black diamond k > 2.7 are provided in Table 8. Table 8: Results of the black diamond test piece (k>2.7) impregnated in the formulation BA-BO. Results of the formulation (test piece) Results (solution) BA All clear completely clarified BA All clear completely clarified BB slightly residual completely clarified BB all clear completely clarified BC all clear completely clarified BC all clear completely clarified BD all clear completely clarified BD all cleared completely clarified BE all cleared completely clarified BE all cleared completely clarified BF all cleared completely clarified BF all cleared completely clarified BG slightly residual completely Clarification BG Slightly residual Complete clarification BH Total removal Complete clarification BH Slight residue Complete clarification BI Slight residue Complete clarification BI Slight residue Complete clarification BJ Total removal Brown residue BJ Clear all brown residue BK Clear all brown residue BK All Clear brown residue BL Clear all brown residue BL Clear all brown residue BM Clear all floating residue BM Clear all residual BN in solution Clear all two-color BN Clear all-color BO Clear all two-color Phase BO All Cleared Two Hue Phases It can be seen that the group comprising Brij 35 or PEG-PPG-PEG block copolymer 143740.doc -53- 201022148 successfully removed all black diamond from the test piece and the resulting solution had no residue. In addition, the composition including DDBSA and Biosoft S-100 successfully removed all black diamond from the test piece. It should be noted that when the formulation was tested with a black diamond test piece having a k value of 2.4, the formulation comprising PEG-PPG-PEG or DDBSA effectively removed all of the black diamond from the test piece and the resulting composition had no residue. Example 6 The following formulations CA and CB were prepared for COD testing using COD combustion techniques. In particular, the test determines the amount of oxygen required to oxidize the reduced compound in the water sample. The oxidant, catalyst and sample were treated at 1 50 °C for 2 hours: Formulation CA: 40 wt% HF (49%), 3 wt% PEG-PPG-PEG block copolymer, 57 wt% water formulation CB : 40 wt% HF (49%), 5 wt% PEG-PPG-PEG block copolymer, 55 wt% water formulation CA and CB diluted with water at 25:1, 500:1 and 1〇〇〇:1 The COD value (expressed in mg/L) was determined. The results are provided in Table 9 below. Table 9: COD values of diluted CA and CB formulations Dilution COD average (mg/L) CA 250:1 307.4 CA 250:1 296.0 CA 500:1 103.2 CA 500:1 148.8 CA 500:1 104.3 CA 1000:1 _ 65.5 CA 1000:1 75.2 143740.doc •54- 201022148 CB 250:1 ----- CB 250:1 ____ 315.2 CB 500:1 224 0 CB 500:1 ——255 8 CB 1000: 1 —~__ 118.6 CB 1000:1 L——_ 101.3 To show the effectiveness of the megasonic wave in removing the material, the preparation of the preparation DA is as follows: 1.5 wt% Formulation DA: 20.1 wt% HF, 57.5 wt% butyl carbitol cyclobutane, 10 wt% Η202, 10.9 wt% water at 35. (: P-SiCOH was immersed in the formulation DA and subjected to dead-sonic treatment for 1 。 minutes. For k values of 3·〇, 2.7'2.4 and 2々p.Sic〇H, all ρ-SiCOH were stripped. There is no residual residue except ❿, and the remaining surface is smooth. Similarly, the use of the dead-sound wave preparation da in the hunger removes the black diamond π from the wafer surface only in the _ clock. Therefore, although this article has been referred to this article The invention has been described in terms of specific aspects, features, and illustrative embodiments of the invention, but it is understood that the invention is not limited by the scope of the invention, but may be extended to and encompass many other aspects, features, and embodiments. It is understood that all such aspects, features, and embodiments are within the spirit and scope of the invention. ^ [Simple description of the drawings] Figure 1 Tungsten wafers in the formulation ε Electron micrograph of the medium after the impregnation. Figure 1 Β 鹤 晶圆 晶圆 在 在 调 调 调 调 调 调 Β Β Β Β Β Β Β Β Β Β Β Β Β Β Β Β Β Β Β Β Β Β Β Β Β Β Β Β Β Β Β Thunderbolt microphotograph; 143740.doc -55 201022148 Figure ID is a tungsten wafer dipped in the formulation AD After the electron micrograph;. 1E and FIG electron micrograph of the wafer W based on the collapse of the impregnated formulation AE 143740.doc • 56-

Claims (1)

201022148 七、申請專利範圍： 1. 種移除組合物，其包含至少一種蝕刻劑、至少一種界 面活化劑/聚合物源、水及視情況至少一種消泡劑。 2. 如凊求項1之移除組合物，其包含消泡劑其中該消泡 劑包含選自由以下組成之群之物質：環氧乙烷/環氧丙烷 嵌段共聚物、醇烷氧基化物、脂肪醇烷氧基化物、磷酸 酯與非離子乳化劑之摻合物、及其組合。 3·如請求項2之移除組合物，其進一步包含至少一種氣化 物源。 4_如請求項2之移除組合物，其進一步包含至少一種螯合 劑。 5. 如請求項2之移除組合物，其進一步包含至少一種螯合 劑及至少一種氣化物源。 6. 如請求項1至5中任一項之移除組合物，其進一步包含至 少一種氧化劑。 7. 如請求項1至5中任一項之移除組合物，其中該至少一種 蝕刻劑包含HF ;且 其中該至少一種界面活化劑/聚合物源包含選自由以下 組成之群之物質：氟烷基界面活化劑、乙氧基化氟界面 活化劑、聚乙二醇、聚丙二醇、聚乙二醇醚、聚丙二醇 醚、羧酸鹽、十二烷基苯磺酸及其鹽、其他直鏈烷基苯 磺酸（LABSA)或其鹽、聚丙烯酸酯聚合物、二壬基苯基 聚氧乙烯、聚矽氧聚合物、經改良之聚矽氧聚合物、乙 炔系二醇、經改良之乙炔系二醇、烷基銨鹽、經改良之 I43740.doc 201022148 烷基銨鹽、烷基酚聚縮水甘油醚、烷基硫酸鈉、烷基硫 酸銨、烷基（CwC^)鲮酸銨鹽、磺基琥珀酸鈉及其酯、 烷基（C^o-C,8)磺酸鈉鹽、二陰離子磺酸鹽界面活化劑、 十六烷基三甲基溴化銨、十六烷基三曱基硫酸氫銨、羧 酸銨、硫酸銨、胺氧化物、队十二烷基_N，N二甲基甜菜 驗、甜菜驗、續基甜菜鹼、烷基銨基丙基硫酸鹽、聚乙 二醇（PEG)、聚環氧乙烷（pE〇)、聚乙烯基吡咯啶酮 (PVP)、經乙基纖維素（HEC)、丙烯醯胺聚合物、聚（丙 烯酸）、羧甲基纖維素（CMC)、羧甲基纖維素鈉 (NaCMC)、羥丙基甲基纖維素、聚乙烯基吡咯啶酮 K30、礼膠粉、乙基纖維素聚合物、丙基纖維素聚合 物、纖維素醚、水溶性樹脂、烷氧基化脂肪醇之磷酸 酯、壬基酚乙氧基化物、脂肪醇烷氧基化物、醇烷氧基 化物、聚氧乙烯二醇十二烷基醚、環氧乙烷/環氧丙烷嵌 段共聚物、及其組合。 8. 如請求項1至5中任一項之移除組合物，其中該至少一種 蝕刻劑包含HF且其中該至少一種界面活化劑/聚合物源 包含選自由以下組成之群之物質：二陰離子磺酸鹽界面 活4匕劑、PPG-PEG-PPG嵌段共聚物、PEG-PPG-PEG嵌段 共聚物、及其組合。 9. 如請求項4或5之移除組合物，其中該至少一種螯合劑包 含選自由以下組成之群之物質··乙醯丙酮酸鹽、1,1,1-三氟-2,4-戊二酮、1,1,1,5,5,5-六氟-2,4-戊二酮、甲酸 鹽、乙酸鹽、雙（三甲基甲矽烷基醯胺）四聚體、甘胺 I43740.doc 201022148 酸、絲胺酸、脯胺酸、亮胺酸、丙胺酸、天冬醯胺、天 冬胺酸、麩胺醯胺、纈胺酸、離胺酸、檸檬酸、乙酸、 馬來酸、草酸、丙二酸、琥珀酸、膦酸、羥基亞乙基二 膦酸（HEDP)、1-羥基乙烷-1,1-二膦酸、氮基-叁（亞曱基 膦酸）、氮基三乙酸、亞胺基二乙酸、依替膦酸 (etidronic acid)、乙二胺、乙二胺四乙酸（EDTA)、（1，2-伸環己基二氮基）四乙酸（CDTA)、尿酸、四乙醇二甲 醚、五曱基二伸乙基三胺（卩\10£丁八）、1，3,5_三嗪-2,4,6· 三硫醇三鈉鹽溶液、1，3,5-三嗪-2,4,6-三硫醇三銨鹽溶 液、二乙基二硫代胺基甲酸鈉、經二取代之二硫代胺基 甲酸鹽、硫酸銨、單乙醇胺（MEA)、Dequest 2000、 Dequest 2010、Dequest 2060、二伸乙基三胺五乙酸、丙 二胺四乙酸、2-羥基吡啶1-氧化物、乙二胺二琥珀酸、 三填酸五納、及其組合。 ίο. 11. 12. 13. 如請求項4或5之移除組合物，其中該至少一種螯合劑包 含膦酸衍生物。 如請求項6之移除組合物，其中該至少一種氣化物源包 含氫氣酸' 鹼金屬氣化物、鹼土金屬氣化物、氯化銨、 烧基氣化錢、及其組合。 如凊求項2之移除組合物，其中該組合物包含hf、至少 一種消泡劑、至少一種二陰離子磺酸鹽界面活化劑、及 水。 如凊求項5之移除組合物，其中該組合物包含HF、氣化 銨、至少一種消泡劑、至少一種二陰離子磺酸鹽界面活 143740.doc 201022148 化劑、至少一種膦酸衍生物、及水。 14. 如請求項5之移除組合物，其進一步包含包含至少一種 氧化劑其中該組合物包含tlF、氯化錄、至少一種消泡 劑至夕一種烧基二苯基氧化物二績酸鹽界面活化劑、 至少一種膦酸衍生物、過氧化物化合物、及水。 15. 如請求項丨之移除組合物，其中該組合物包含hf、水及 至少一種界面活化劑/聚合物源，該界面活化劑/聚合物 、原選自由PEG-PPG-PEG嵌段共聚物、ppg_peG-PPG嵌段 八聚物聚氧乙烯二醇十二燒基縫界面活化劑、及其組 合組成之群。 16. 如明求項1至5及15中任一項之移除組合物其中該組合 物進步包含選自由以下組成之群之材料殘餘物：钱刻 後殘餘物、低_k介電材料殘餘物、高_k介電材料殘餘 物、障壁層材料殘餘物、鐵電殘餘物、氮化物殘餘物、 矽化物殘餘物、氧化物殘餘物、含聚合物之累積殘餘 物、ARC材料殘餘物、經摻雜區域之殘餘物、其他材料 殘餘物、及其組合。 17. -種再循環利用微電子裝置結構之方法，該方法包含： 使微電子裝置結構與前述請求項中任—項之移除組合物 在足以實質上自該微電子裝置結構移除至少一種材料之 條件下接觸足夠_以獲得可再㈣利用或可再使用之 微電子裝置基板，該微電子I置結構包含微電子裝置基 板及該至少-種選自由以下組成之群之可移除材料鐵 刻後殘餘物、低·k介電質、高·k介電質、餘刻終止材 143740.doc -4- 201022148 料、金屬堆疊材料、障壁層材料、鐵電材料梦化物材 料、氮化物材料、氧化物材料、光阻劑、底部抗反射塗 層（BARC)、犧牲性抗反射塗層（SARC)、含聚合物之累 積物、其他材料、經摻雜區域、及其組合。 18. 如請求項17之方法，其進一步包含將至少一種可沈積材 料沈積於該可再使用基板上，其中該至少—種可沈㈣ 料選自由以下組成之群：低_k介電質、高_k介電質、蝕 刻終止材料、金屬堆叠材料、障壁層材料、鐵電材料、 矽化物材料、氮化物材料、氧化物材料、光阻劑底部 抗反射塗層（BARC)、犧牲性抗反射塗層（sarc)、其他 材料、及其組合。 19. 種套組’其在一或多個容器中包含一或多種用於形成 移除組合物之以下試劑，其中該移除組合物包含至少一 種姓刻劑、至少一種界面活化劑/聚合物源、水、視情況 至少種螯合劑、視情況至少一種氧化劑、視情況至少 一種氣化物源、及視情況至少一種消泡劑，其中該套組 適於形成適用於將至少一種可移除材料自其上具有該可 移除材料之微電子裝置結構移除的移除組合物，該可移 除材料選自由以下組成之群：蝕刻後殘餘物、低_k介電 質、高-k介電質、蝕刻終止材料、金屬堆疊材料、障壁 層材料、鐵電材料、矽化物材料、氮化物材料、氧化物 材料、光阻劑、底部抗反射塗層（BARC)、犧牲性抗反射 塗層（SARC)、含聚合物之累積物、其他材料、經摻雜區 域、及其組合。 143740.doc201022148 VII. Patent Application Range: 1. A removal composition comprising at least one etchant, at least one interface activator/polymer source, water, and optionally at least one antifoaming agent. 2. The removal composition of claim 1, comprising an antifoaming agent, wherein the antifoaming agent comprises a substance selected from the group consisting of: an ethylene oxide/propylene oxide block copolymer, an alcohol alkoxy group Blends of fatty alcohol alkoxylates, phosphates and nonionic emulsifiers, and combinations thereof. 3. The removal composition of claim 2, further comprising at least one source of gasification. 4_ The removal composition of claim 2, further comprising at least one chelating agent. 5. The removal composition of claim 2, further comprising at least one chelating agent and at least one vapor source. 6. The removal composition of any one of claims 1 to 5, further comprising at least one oxidizing agent. The removal composition of any one of claims 1 to 5, wherein the at least one etchant comprises HF; and wherein the at least one interface activator/polymer source comprises a substance selected from the group consisting of: fluorine Alkyl interface activator, ethoxylated fluorine interface activator, polyethylene glycol, polypropylene glycol, polyethylene glycol ether, polypropylene glycol ether, carboxylate, dodecylbenzenesulfonic acid and its salts, other straight Alkylbenzenesulfonic acid (LABSA) or a salt thereof, polyacrylate polymer, dimercaptophenyl polyoxyethylene, polyoxynoxy polymer, modified polyoxyl polymer, acetylene glycol, improved Acetylene glycol, alkyl ammonium salt, modified I43740.doc 201022148 alkyl ammonium salt, alkylphenol polyglycidyl ether, sodium alkyl sulfate, ammonium alkyl sulfate, alkyl (CwC) ammonium citrate Salt, sodium sulfosuccinate and ester thereof, alkyl (C^oC, 8) sodium sulfonate, dianion sulfonate interface activator, cetyltrimethylammonium bromide, cetyl Ammonium thiosulfate, ammonium carboxylate, ammonium sulfate, amine oxide, group dodecyl _N, N dimethyl beet, sweet Test, contigine betaine, alkyl ammonium propyl sulfate, polyethylene glycol (PEG), polyethylene oxide (pE 〇), polyvinyl pyrrolidone (PVP), ethyl cellulose ( HEC), acrylamide polymer, poly(acrylic acid), carboxymethyl cellulose (CMC), sodium carboxymethyl cellulose (NaCMC), hydroxypropyl methylcellulose, polyvinylpyrrolidone K30, ritual Rubber powder, ethyl cellulose polymer, propyl cellulose polymer, cellulose ether, water-soluble resin, phosphate of alkoxylated fatty alcohol, nonylphenol ethoxylate, fatty alcohol alkoxylate, Alcohol alkoxylates, polyoxyethylene glycol lauryl ethers, ethylene oxide/propylene oxide block copolymers, and combinations thereof. The removal composition of any one of claims 1 to 5, wherein the at least one etchant comprises HF and wherein the at least one interface activator/polymer source comprises a substance selected from the group consisting of: dianions Sulfonate interface 4 tanning agent, PPG-PEG-PPG block copolymer, PEG-PPG-PEG block copolymer, and combinations thereof. 9. The removal composition of claim 4 or 5, wherein the at least one chelating agent comprises a substance selected from the group consisting of acetylacetonate, 1,1,1-trifluoro-2,4- Pentanedione, 1,1,1,5,5,5-hexafluoro-2,4-pentanedione, formate, acetate, bis(trimethylformamidine) tetramer, Gan Amine I43740.doc 201022148 Acid, serine, valine, leucine, alanine, aspartame, aspartic acid, glutamine, valine, lysine, citric acid, acetic acid, Maleic acid, oxalic acid, malonic acid, succinic acid, phosphonic acid, hydroxyethylidene diphosphonic acid (HEDP), 1-hydroxyethane-1,1-diphosphonic acid, nitrogen-niobium (phosphonium phosphine) Acid), nitrogen triacetic acid, iminodiacetic acid, etidronic acid, ethylenediamine, ethylenediaminetetraacetic acid (EDTA), (1,2-cyclohexyldiazepine)tetraacetic acid (CDTA), uric acid, tetraethanol dimethyl ether, pentadecyl diethylidene triamine (卩\10£丁八), 1,3,5-triazine-2,4,6· trithiol trisodium Salt solution, 1,3,5-triazine-2,4,6-trithiol triammonium salt solution, sodium diethyldithiocarbamate, Dithiocarbamate, ammonium sulfate, monoethanolamine (MEA), Dequest 2000, Dequest 2010, Dequest 2060, diethyltriamine pentaacetic acid, propylenediaminetetraacetic acid, 2-hydroxypyridine 1-oxidation , ethylenediamine disuccinic acid, trisodium pentoxide, and combinations thereof. 11. The removal composition of claim 4 or 5, wherein the at least one chelating agent comprises a phosphonic acid derivative. The removal composition of claim 6, wherein the at least one vapor source comprises hydrogen acid 'alkali metal vapor, alkaline earth metal vapor, ammonium chloride, burnt gas, and combinations thereof. The composition of claim 2, wherein the composition comprises hf, at least one antifoaming agent, at least one dianionic sulfonate interface activator, and water. The removal composition of claim 5, wherein the composition comprises HF, ammonium sulfate, at least one antifoaming agent, at least one dianion sulfonate interface 143740.doc 201022148, at least one phosphonic acid derivative And water. 14. The removal composition of claim 5, further comprising at least one oxidizing agent, wherein the composition comprises tlF, chlorinated, at least one antifoaming agent, and a bismuth diphenyl oxide dibasic acid salt interface An activator, at least one phosphonic acid derivative, a peroxide compound, and water. 15. The removal composition of claim </ RTI> wherein the composition comprises hf, water, and at least one interfacial activator/polymer source, the interfacial activator/polymer, selected from the group consisting of PEG-PPG-PEG block copolymerization a group of ppg_peG-PPG block octamer polyoxyethylene diol twelve-burning base interfacial activator, and combinations thereof. 16. The removal composition of any one of clauses 1 to 5 and 15, wherein the composition progress comprises a material residue selected from the group consisting of: a post-mortem residue, a low-k dielectric material residue , high-k dielectric material residue, barrier layer material residue, ferroelectric residue, nitride residue, telluride residue, oxide residue, polymer-containing cumulative residue, ARC material residue, Residues of the doped regions, other material residues, and combinations thereof. 17. A method of recycling a structure of a microelectronic device, the method comprising: causing a microelectronic device structure and the removal composition of any of the preceding claims to be at least one substantially removed from the structure of the microelectronic device Contacting the material under conditions sufficient to obtain a reusable or reusable microelectronic device substrate comprising a microelectronic device substrate and the at least one removable material selected from the group consisting of Residue after iron engraving, low-k dielectric, high-k dielectric, residual termination material 143740.doc -4- 201022148 material, metal stack material, barrier layer material, ferroelectric material dream material, nitride Materials, oxide materials, photoresists, bottom anti-reflective coatings (BARC), sacrificial anti-reflective coatings (SARC), polymer-containing buildups, other materials, doped regions, and combinations thereof. 18. The method of claim 17, further comprising depositing at least one depositable material on the reusable substrate, wherein the at least one of the materials is selected from the group consisting of: a low-k dielectric, High_k dielectric, etch stop material, metal stack material, barrier layer material, ferroelectric material, germanide material, nitride material, oxide material, photoresist anti-reflective coating (BARC), sacrificial resistance Reflective coating (sarc), other materials, and combinations thereof. 19. A kit comprising one or more of the following agents for forming a removal composition in one or more containers, wherein the removal composition comprises at least one surname, at least one interfacial activator/polymer Source, water, optionally at least one chelating agent, optionally at least one oxidizing agent, optionally at least one vapor source, and optionally at least one antifoaming agent, wherein the kit is suitable for forming at least one removable material a removal composition removed from the structure of the microelectronic device having the removable material, the removable material being selected from the group consisting of: post-etch residues, low-k dielectric, high-k Electrochemistry, etch stop material, metal stack material, barrier layer material, ferroelectric material, germanide material, nitride material, oxide material, photoresist, bottom anti-reflective coating (BARC), sacrificial anti-reflective coating (SARC), polymer-containing buildup, other materials, doped regions, and combinations thereof. 143740.doc
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