TWI791498B - 用來移除在半導體基材上的殘餘物之清潔組成物 - Google Patents
用來移除在半導體基材上的殘餘物之清潔組成物 Download PDFInfo
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- TWI791498B TWI791498B TW107109658A TW107109658A TWI791498B TW I791498 B TWI791498 B TW I791498B TW 107109658 A TW107109658 A TW 107109658A TW 107109658 A TW107109658 A TW 107109658A TW I791498 B TWI791498 B TW I791498B
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- 239000005297 pyrex Substances 0.000 description 1
- HNJBEVLQSNELDL-UHFFFAOYSA-N pyrrolidin-2-one Chemical compound O=C1CCCN1 HNJBEVLQSNELDL-UHFFFAOYSA-N 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
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- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 description 1
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- ISIJQEHRDSCQIU-UHFFFAOYSA-N tert-butyl 2,7-diazaspiro[4.5]decane-7-carboxylate Chemical compound C1N(C(=O)OC(C)(C)C)CCCC11CNCC1 ISIJQEHRDSCQIU-UHFFFAOYSA-N 0.000 description 1
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- LRGJRHZIDJQFCL-UHFFFAOYSA-M tetraethylazanium;hydroxide Chemical compound [OH-].CC[N+](CC)(CC)CC LRGJRHZIDJQFCL-UHFFFAOYSA-M 0.000 description 1
- UWHCKJMYHZGTIT-UHFFFAOYSA-N tetraethylene glycol Chemical compound OCCOCCOCCOCCO UWHCKJMYHZGTIT-UHFFFAOYSA-N 0.000 description 1
- BSYVTEYKTMYBMK-UHFFFAOYSA-N tetrahydrofurfuryl alcohol Chemical compound OCC1CCCO1 BSYVTEYKTMYBMK-UHFFFAOYSA-N 0.000 description 1
- LUVHDTDFZLTVFM-UHFFFAOYSA-M tetramethylazanium;chlorate Chemical compound [O-]Cl(=O)=O.C[N+](C)(C)C LUVHDTDFZLTVFM-UHFFFAOYSA-M 0.000 description 1
- ZRVXFJFFJZFRLQ-UHFFFAOYSA-M tetramethylazanium;iodate Chemical compound [O-]I(=O)=O.C[N+](C)(C)C ZRVXFJFFJZFRLQ-UHFFFAOYSA-M 0.000 description 1
- HLQAWDQQEJSALG-UHFFFAOYSA-M tetramethylazanium;periodate Chemical compound C[N+](C)(C)C.[O-]I(=O)(=O)=O HLQAWDQQEJSALG-UHFFFAOYSA-M 0.000 description 1
- LPSKDVINWQNWFE-UHFFFAOYSA-M tetrapropylazanium;hydroxide Chemical compound [OH-].CCC[N+](CCC)(CCC)CCC LPSKDVINWQNWFE-UHFFFAOYSA-M 0.000 description 1
- IMFACGCPASFAPR-UHFFFAOYSA-N tributylamine Chemical compound CCCCN(CCCC)CCCC IMFACGCPASFAPR-UHFFFAOYSA-N 0.000 description 1
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 description 1
- JLGLQAWTXXGVEM-UHFFFAOYSA-N triethylene glycol monomethyl ether Chemical compound COCCOCCOCCO JLGLQAWTXXGVEM-UHFFFAOYSA-N 0.000 description 1
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- AQLJVWUFPCUVLO-UHFFFAOYSA-N urea hydrogen peroxide Chemical compound OO.NC(N)=O AQLJVWUFPCUVLO-UHFFFAOYSA-N 0.000 description 1
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Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B08—CLEANING
- B08B—CLEANING IN GENERAL; PREVENTION OF FOULING IN GENERAL
- B08B3/00—Cleaning by methods involving the use or presence of liquid or steam
- B08B3/04—Cleaning involving contact with liquid
- B08B3/08—Cleaning involving contact with liquid the liquid having chemical or dissolving effect
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/0005—Other compounding ingredients characterised by their effect
- C11D3/0042—Reducing agents
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/02—Inorganic compounds ; Elemental compounds
- C11D3/04—Water-soluble compounds
- C11D3/044—Hydroxides or bases
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/02—Inorganic compounds ; Elemental compounds
- C11D3/04—Water-soluble compounds
- C11D3/046—Salts
-
- 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
- C11D3/12—Water-insoluble compounds
- C11D3/1213—Oxides or hydroxides, e.g. Al2O3, TiO2, CaO or Ca(OH)2
-
- 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
- C11D3/2003—Alcohols; Phenols
- C11D3/2006—Monohydric alcohols
-
- 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
- C11D3/2003—Alcohols; Phenols
- C11D3/2041—Dihydric alcohols
-
- 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
- C11D3/26—Organic compounds containing nitrogen
- C11D3/28—Heterocyclic compounds containing nitrogen in the ring
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/16—Organic compounds
- C11D3/26—Organic compounds containing nitrogen
- C11D3/30—Amines; Substituted amines ; Quaternized amines
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/16—Organic compounds
- C11D3/26—Organic compounds containing nitrogen
- C11D3/33—Amino carboxylic acids
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/16—Organic compounds
- C11D3/34—Organic compounds containing sulfur
- C11D3/3409—Alkyl -, alkenyl -, cycloalkyl - or terpene sulfates or sulfonates
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/16—Organic compounds
- C11D3/34—Organic compounds containing sulfur
- C11D3/3427—Organic compounds containing sulfur containing thiol, mercapto or sulfide groups, e.g. thioethers or mercaptales
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/16—Organic compounds
- C11D3/34—Organic compounds containing sulfur
- C11D3/349—Organic compounds containing sulfur additionally containing nitrogen atoms, e.g. nitro, nitroso, amino, imino, nitrilo, nitrile groups containing compounds or their derivatives or thio urea
-
- 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
- C11D3/43—Solvents
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D7/00—Compositions of detergents based essentially on non-surface-active compounds
- C11D7/02—Inorganic compounds
- C11D7/04—Water-soluble compounds
- C11D7/06—Hydroxides
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D7/00—Compositions of detergents based essentially on non-surface-active compounds
- C11D7/02—Inorganic compounds
- C11D7/04—Water-soluble compounds
- C11D7/10—Salts
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D7/00—Compositions of detergents based essentially on non-surface-active compounds
- C11D7/02—Inorganic compounds
- C11D7/20—Water-insoluble oxides
-
- C—CHEMISTRY; METALLURGY
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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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Abstract
本揭露係有關於一清潔組成物,其含有1)至少一氧化還原劑;2)至少一水溶性有機溶劑;3)至少一含金屬之添加劑;4)至少一環狀胺,及5)水。
Description
相關申請案之對照參考資料 本申請案主張於2017年3月24日申請之美國臨時申請序號第62/475,947號案之優先權,此案在此被完整併入以供參考。 1.揭露領域
本揭露係有關於用於半導體基材之新穎清潔組成物及清潔半導體基材之方法。更特別地,本揭露係有關於在電漿蝕刻沉積於基材上之金屬層或介電材料層之後用於半導體基材,及於經由電漿灰化方法移除本體殘餘物之後移除留於基材上的殘餘物之清潔組成物。
2.背景技藝探討 於製造積體電路裝置,光阻劑係作為一中間遮罩,其係用於藉由一系列之微影術及電漿蝕刻步驟將一光罩的原始遮罩圖案轉移至晶圓基材上。積體電路裝置製造方法的基本步驟之一係自晶圓基材移除經圖案化之光阻劑膜。一般,此步驟係藉由二方法實行。
一方法涉及一濕式剝除步驟,其中,使經光阻劑覆蓋之基材與主要由一有機溶劑及一胺組成之一光阻劑剝除劑溶液接觸。但是,剝除劑溶液無法完全且可信賴地移除光阻劑膜,特別是若光阻劑膜於製造期間已曝露於紫外線輻射及電漿處理。某些光阻劑膜藉由此等處理已變成高度交聯,且係更難以溶於剝除劑溶液中。此外,用於此等傳統濕式剝除方法之化學品有時對於移除在以含鹵素之氣體將金屬或氧化物層電漿蝕刻期間形成之無機或有機金屬殘餘材料係無效。
移除光阻劑膜之一另外方法涉及將一經光阻劑塗覆之基材曝路於氧系電漿(oxygen-based plasma),以便於一稱為電漿灰化之方法中將光阻膜自基材燒掉。但是,電漿灰化於移除如上所示之電漿蝕刻副產物並非完全有效。相反地,此等電漿蝕刻副產物之移除典型上係藉由其後將經處理之金屬及介電薄膜曝露於某些清潔溶液而完成。
金屬基材一般係易腐蝕。例如,諸如鋁、銅、鋁-銅合金、氮化鎢、鎢(W)、鈷(Co)、氧化鈦、其它金屬及金屬氮化物之基材會輕易腐蝕,且介電質[ILD,ULK]會藉由使用傳統清潔化學品而非所欲地蝕刻。此外,積體電路裝置製造商容忍之腐蝕量因為裝置幾何縮小而逐漸變得更小。
同時,當殘餘物變得更難以移除且腐蝕需被控制至更低量,清潔溶液需為安全上係安全且係環境友善。
因此,清潔溶液對於移除電漿蝕刻及電漿灰化殘餘物需為有效,且對於所有經曝露之基材材料亦需為非腐蝕性。
揭露概要 本揭露係有闗於非腐蝕性清潔組成物,其可於一多步驟製造方法之一中間步驟,用於自一半導體基材移除殘餘物(例如,電漿蝕刻及/或電漿灰化殘餘物)。此等殘餘物包括諸如殘餘光阻劑之有機化合物;有機金屬化合物;諸如鋁氧化物(AlOx)、鈦氧化物(TiOx)、鋯氧化物(ZrOx)、鉭氧化物(TaOx),及鉿氧化物(HfOx)之金屬氧化物(其等可自露出之金屬以反應副產物形成);諸如鋁(Al)、鋁/銅之合金、銅(Cu)、鈦(Ti)、鉭(Ta)、鎢(W),及鈷(Co)之金屬;諸如氮化鋁(AlN)、鋁氧氮化物(AlOxNy)、氮化鈦(TiN)、氮化鉭(TaN),及氮化鎢(WN)之金屬氮化物;此等之合金;及其它材料之一系列相對較不可溶混合物。此處所述清潔組成物之一優點係其可清理所遭遇且對於露出之基材材料(例如,露出之金屬(諸如,鋁、鋁/銅之合金、銅、鈦、鉭、鎢,及鈷)、金屬氮化物(諸如,氮化鈦、氮化鉭,及氮化鎢),及其等之合金)一般係非.腐蝕性之一廣範圍的殘餘物。
於一方面,本揭露特徵係一種清潔組成物,其含有 1)至少一氧化還原劑; 2)至少一水溶性有機溶劑; 3)至少一含金屬之添加劑; 4)至少一環狀胺;及 5)水。
本揭露特徵亦係一種清潔來自一半導體基材的殘餘物之方法。此方法包括將含有蝕刻後殘餘物及/或灰化後殘餘物之一半導體基材與此處所述之一清潔組成物接觸。例如,此方法可包括步驟:(A)提供含有蝕刻後及/或灰化後的殘餘物之一半導體基材;(B)將該半導體基材與此處所述之一清潔組成物接觸;(C)以一適合沖洗溶劑沖洗該半導體基材;及(D)選擇性地,藉由移除沖洗溶劑且不會折衷該半導體基材的完整性之任何手段乾燥該半導體基材。
揭露之詳細說明 如此處中所定義,除非另作說明,表示之所有百分率需瞭解係清潔組成物總重量之重量百分率。除非另作說明,周圍溫度係定義為於約16與約27攝式溫度(°C)之間,諸如,25°C。
術語"層"及"膜"係交替使用。
如於此處所定義,一“水溶性”物質(例如,一水溶性之醇、酮、酯、碸,或醚)係指於25°C之水中具有至少5重量%之溶解度的一物質。
本揭露之一實施例係有關於一種非腐蝕性清潔組成物,其包括: 1)至少一氧化還原劑; 2)至少一水溶性有機溶劑(例如,選自由水溶性醇、水溶性酮、水溶性酯、水溶性碸,及水溶性醚所組成群組之一水溶性有機溶劑); 3)至少一含金屬之添加劑; 4)至少一環狀胺;及 5)水。
本揭露之組成物含有至少一氧化還原劑,其被認為係助於溶解半導體表面上之諸如光阻劑殘餘物、金屬殘餘物,及金屬氧化物殘餘物之殘餘物。於此處使用時,術語“氧化還原劑”係指於一半導體清潔方法中誘發氧化及/或還原之一化合物。一適合氧化還原劑的一範例係羥基胺。於某些實施例,此處所述之氧化還原劑或清潔組成物不包括過氧化物(例如,過氧化氫)。
於某些實施例,本揭露之組成物包括至少約0.5重量%(例如,至少約1重量%,至少約2重量%,至少約3重量%,或至少約5重量%)及/或至多約20重量%(例如,至多約17重量%,至多約15重量%,至多約12重量%,或至多約10重量%)之氧化還原劑。
於某些實施例,本揭露之組成物含有至少一種(例如,二、三、四=力或更多種)水溶性有機溶劑,諸如,選自由水溶性醇、水溶性酮、水溶性酯、水溶性碸,及水溶性醚(例如,二醇二醚)所組成群組之一水溶性有機溶劑。
水溶性醇的種類不受限地包括烷二醇(不受限地包括伸烷基二醇、二醇、烷氧醇(不受限地包括二醇單醚)、飽和脂族單羥醇、不飽和非芳香族羥醇,及含有一環結構之低分子量醇(例如,具有少於500克/莫耳,少於400克/莫耳,少於300克/莫耳,少於200克/莫耳,或少於100克/莫耳之分子量者)。
水溶性烷二醇的例子不受限地包括2-甲基-1,3-丙二醇、1,3-丙二醇、2,2-二甲基-1,3-丙二醇、1,4-丁二醇、1,3-丁二醇、1,2-丁二醇、2,3-丁二醇、頻哪醇,及伸烷基二醇。
水溶性伸烷基二醇的例子不受限地包括乙二醇、丙二醇、己二醇、二乙二醇、二丙二醇、三乙二醇,及四乙二醇。
水溶性烷氧醇的例子不受限地包括3-甲氧基-3-甲基-1-丁醇、3-甲氧基-1-丁醇、1-甲氧基-2-丁醇,及水溶性伸烷基二醇單醚。
水溶性伸烷基二醇單醚的例子不受限地包括乙二醇單甲醚、乙二醇單乙醚、乙二醇單正丙醚、乙二醇單異丙醚、乙二醇單正丁醚、二乙二醇單甲醚、二乙二醇單乙醚、二乙二醇單丁醚、三乙二醇單甲醚、三乙二醇單乙醚、三乙二醇單丁醚、1-甲氧基-2-丙醇、2-甲氧基-1-丙醇、1-乙氧基-2-丙醇、2-乙氧基-1-丙醇、丙二醇單正丙醚、二丙二醇單甲醚、二丙二醇單乙醚、二丙二醇單正丙醚、三丙二醇單乙醚、三丙二醇單甲醚、乙二醇單苯甲醚,及二乙二醇單苯甲醚。
水溶性飽和脂族單羥基醇的例子不受限地包括甲醇、乙醇、正丙醇、異丙醇、1-丁醇、2-丁醇、異丁醇、第三丁醇、2-戊醇、第三戊醇,及1-己醇。
水溶性不飽和非芳香族單羥基醇的例子不受限地包括烯丙醇、炔丙醇、2-丁烯醇、3-丁烯醇,及4-戊烯-2-醇。
含有一環結構之水溶性低分子量醇的例子不受限地包括四氫呋喃甲醇、呋喃甲醇,及1,3-環戊二醇。
水溶性酮的例子不受限地包括丙酮(acetone)、丙酮(propanone)、環丁酮、環戊酮、環己酮、二丙酮醇、2-丁酮、2,5-己二酮、1,4-環己二酮、3-羥基苯乙酮,及1,3-環己二酮。
水溶性酯的例子不受限地包括乙酸乙酯,及二醇單酯(諸如,乙二醇單乙酸酯、二乙二醇單乙酸酯,及二醇單醚單酯,諸如,丙二醇單甲醚乙酸酯、乙二醇單甲醚乙酸酯、丙二醇單乙醚乙酸酯,及乙二醇單乙醚乙酸酯)。
水溶性碸的例子不受限地包括環丁碸及二甲碸。
水溶性醚的例子不受限地包括烷氧醇(例如,伸烷基二醇單醚),諸如,上述者。
於某些實施例,本揭露之清潔組成物包括至少約60重量%(例如,至少約65重量%,至少約70重量%,或至少約75重量%)及/或至多約95重量%(例如,至多約90重量%,至多約85重量%,或至多約80重量%)之至少一水溶性有機溶劑。
本揭露之清潔組成物進一步包括水。較佳地,水係去離子及超純,不含有有機污染物,且具有約4至約17百萬歐姆之一最小電阻。更佳地,水之電阻係至少17百萬歐姆。
於某些實施例,本揭露之清潔組成物包括至少約5重量%(例如,至少約8重量%,至少約12重量%,或至少約16重量%)及/或至多約28重量%(例如,至多約24重量%,至多約20重量%,或至多約18重量%)之水。
被考慮用於本揭露之清潔組成物中的含金屬之添加劑包括選自2A族金屬、3B族金屬、4B族金屬、5B族金屬,及鑭系金屬之金屬。於某些實施例,金屬係Ca、Ba、Ti、Hf、Sr、La、Ce、W、V、Nb,或Ta。於某些實施例,金屬係選自4B族金屬(諸如,Ti或Hf)。
含金屬之添加劑可呈金屬鹵化物、金屬氫氧化物、金屬硼化物、金屬烷氧化物、金屬氧化物,或含金屬之銨鹽的型式。於某些實施例,含金屬之添加劑係銨鹽。銨鹽可為具有化學式(I):(NH4
)m
MXn
(I)之鹽;其中,m係1、2、3,或4;n係1、2、3、4、5,或6;M係一金屬離子(諸如,2A族金屬、3B族金屬、4B族金屬、5B族金屬,或鑭系金屬之一離子);且X係一鹵離子(例如,F、Cl、Br,或I)。於某些實施例,含金屬之添加劑係六氟鈦酸銨((NH4
)2
TiF6
)。含金屬之添加劑的例子可包括硼化鎢、Ca(OH)2
、BaCl2
、SrCl2
、LaCl3
、CeCl3
、(NH4
)2
TiF6
、BaTiO3
、Ti(OEt)4
、Ti(OCH(CH3
)2
)4
、HfO2
、V2
O5
、Nb2
O5
,及TaF3
。
於某些實施例,含金屬之添加劑可為清潔組成物之至少約0.001重量%(例如,至少約0.002重量%,至少約0.004重量%,至少約0.006重量%,至少約0.008重量%,或至少約0.01重量%)及/或至多約0.5重量%(例如,至多約0.4重量%,至多約0.3重量%,至多約0.2重量%,至多約0.1重量%,至多約0.08重量%,至多約0.06重量%,至多約0.04重量%,至多約0.02重量%,或至多約0.01重量%)的量。不受理論約束,相信於一清潔組成物中包括一如上特定量的含金屬之添加劑可降低組成物之腐蝕作用,即,降低清潔組成物對在清潔處理期間不打算被移除之露出基材材料(例如,露出之金屬或介電材料)的蝕刻速率。
一般,本揭露之清潔組成物可包括至少一種(例如,二、三,或四種)環狀胺。於某些實施例,此至少一種環狀胺包括具有化學式(I)之環狀胺:(I), 其中,n係1、2,或3;m係1、2,或3;R1
-R10
之每一者獨立地係H、C1
-C6
烷基,或芳基;且L係-O-、-S-、-N(Ra
)-,或-C(Ra
Rb
)-,其中,Ra
及Rb
之每一者獨立地係H、C1
-C6
烷基,或芳基;且R11
係H或與Ra
一起形成於L與和R11
附接之C原子間的一二級鍵結。於此處使用時,術語“C1-6
烷基”係指可為直鏈或分支且可具有1至6個碳原子之一飽和烴基團。於此處使用時,術語“芳基”係指具有一或多個芳香族基團(例如,二或更多個經稠合之芳香族環)之一烴基團。於某些實施例,芳基基團可具有6-10個環碳。
於某些實施例,化學式(I)中之L係-N(Ra
)-。於此等實施例,n可為2;m可為1或3;R1
-R10
之每一者可為H;且R11
與Ra
一起可形成於L與和R11
附接之C間的一二級鍵結。此等胺之例子包括1,8-二氮雜二環[5.4.0]-7-十一烯(DBU;)及1,5-二氮雜二環[4.3.0]-5-壬烯(DBN;)。
不受理論約束,相信此處所述之環狀胺可降低主要以有機溶劑(例如,含有從約60重量%至約95重量%之有機溶劑s)為主之一清潔組成物的腐蝕作用。例如,環狀胺可助於降低此一清潔組成物對在清潔處理期間不打算被移除之露出基材材料(例如,露出之金屬(諸如,鈷)或介電材料)的蝕刻速率。
於某些實施例,環狀胺可為清潔組成物之至少約0.1重量%(例如,至少約0.2重量%,至少約0.3重量%,至少約0.4重量%,至少約0.5重量%,至少約0.6重量%,至少約0.7重量%,至少約0.8重量%,至少約0.9重量%,或至少約1重量%)及/或至多約2重量%(例如,至多約1.9重量%,至多約1.8重量%,至多約1.7重量%,至多約1.6重量%,至多約1.5重量%,至多約1.4重量%,至多約1.3重量%,至多約1.2重量%,或至多約1.1重量%)的量。不受理論約束,相信於一清潔組成物中含有如上特定量之此處所述的環狀胺可降低組成物之腐蝕作用,即,降低清潔組成物對在清潔處理期間不打算被移除之露出基材材料(例如,露出之金屬(諸如,鈷)或介電材料)的蝕刻速率。
本揭露之清潔組成物可選擇性地含有至少一種(例如,二、三,或四種)用以改良其等之清潔能力(例如,移除蝕刻或灰化殘餘物)及/或降低其等之腐蝕作用的清潔添加劑。於某些實施例,清潔添加劑可為一含硫之添加劑或一胺基酸。於某些實施例,清潔組成物可包括一含硫之添加劑及一胺基酸二者。
被考慮用於本揭露之清潔組成物的含硫之添加劑不受特別限制。於某些實施例,含硫之添加劑係承載一硫醇部份(即,SH)或硫醚部份(例如,SR,其中,R係C1
-C10
烷基)之一分子。於某些實施例,含硫之添加劑可為含有一硫醇或硫醚部份之一醇、一酸、一胺,或一雜環狀化合物。含硫之添加劑的例子不受限地包括3-胺基-5-巰基-1H-1,2,4-三唑;β-巰基乙醇;3-胺基-5-甲硫基-1H-1,2,4-三唑;1-苯基-1H-四唑-5-硫醇;4-甲基-4H-1,2,4-三唑-3-硫醇;2-吡啶硫醇;3-巰基-丙酸等。於某些實施例,含硫之添加劑可排除含硫之有機酸。
於某些實施例,含硫之添加劑可為清潔組成物之至少約0.01重量%(例如,至少約0.02重量%,至少約0.04重量%,至少約0.05重量%,至少約0.06重量%,或至少約0.08重量%)及/或至多約0.15重量%(例如,至多約0.14重量%,至多約0.12重量%,至多約0.1重量%,至多約0.08重量%,或至多約0.07重量%)的量。不受理論約束,相信於一清潔組成物中包括如上特定量的含硫之添加劑可改良組成物用於移除蝕刻後及/或灰化後之殘餘物的清潔能力及/或降低清潔組成物對在清潔處理期間不打算被移除之露出基材材料(例如,露出之金屬或介電材料)的蝕刻速率。
於某些實施例,清潔添加劑可包括至少一種(例如,二、三,或四種)胺基酸(例如,甘胺酸)。胺基酸可為一天然發生之胺基酸或非天然發生之胺基酸(例如,一合成胺基酸)。胺基酸可為一D-或L-胺基酸。
於某些實施例,胺基酸可為清潔組成物之至少約0.01重量%(例如,至少約0.02重量%,至少約0.04重量%,至少約0.05重量%,至少約0.06重量%,或至少約0.08重量%)及/或至多約0.15重量%(例如,至多約0.14重量%,至多約0.12重量%,至多約0.1重量%,至多約0.08重量%,或至多約0.07重量%)的量。不欲受理論約束,相信於一清潔組成物中包括上述特定量之胺基酸可改良組成物對於移除蝕刻後及/或灰化後之殘餘物的清潔能力及/或降低清潔組成物對在清潔處理期間不打算被移除之露出基材材料(例如,露出之金屬或介電材料)的蝕刻速率。
於某些實施例,本揭露之清潔組成物可含有一或多種(例如,二、三,或四種)有機酸。有機酸可在上述清潔添加劑(例如,含硫之添加劑或胺基酸)存在中或缺乏時用於清潔組成物。被考慮用於本揭露之清潔組成物的有機酸包括羧酸及磺酸。被考慮用於本揭露之組成物的例示羧酸不受限地包括單羧酸、二羧酸、三羧酸、單羧酸之α-羥基酸及β-羥基酸、二羧酸之α-羥基酸或β-羥基酸,及三羧酸之α-羥基酸及β-羥基酸。適合羧酸的例子不受限地包括馬來酸、福馬酸、乳酸、乙醇酸、草酸、酒石酸、琥珀酸,及苯甲酸。適合磺酸的例子不受限地包括甲磺酸、三氟甲磺酸、乙磺酸、三氟乙磺酸、全氟乙磺酸、全氟(乙氧基乙烷)磺酸、全氟(甲氧基乙烷)磺酸、十二烷基磺酸、全氟十二烷基磺酸、丁磺酸、全氟丁磺酸、丙磺酸、全氟丙磺酸、辛磺酸、全氟辛磺酸、甲烷二磺酸、2-甲基丙磺酸、環己磺酸、樟腦磺酸、全氟己磺酸、乙烷二磺酸、苯甲磺酸、羥基苯基甲磺酸、萘基甲磺酸、降冰片烷磺酸、苯磺酸、氯苯磺酸、溴苯磺酸、氟苯磺酸、羥基苯磺酸、硝基苯磺酸、2-羥基-5-磺基苯甲酸、苯二磺酸、甲苯磺酸(例如,對-甲苯磺酸)、甲基氯苯磺酸、十二烷基苯磺酸、丁基苯磺酸、環己基苯磺酸、三硝基苯磺酸、二氯苯磺酸、二溴苯磺酸,及2,4,5-三氯苯磺酸。
於某些實施例,有機酸可為清潔組成物之至少約0.01重量%(例如,至少約0.05重量%,至少約0.1重量%,至少約0.12重量%,至少約0.14重量%,至少約0.16重量%,至少約0.18重量%,或至少約0.2重量%)及/或至多約0.5重量%(例如,至多約0.4重量%,至多約0.3重量%,至多約0.2重量%,至多約0.18重量%,或至多約0.16重量%)的量。不欲受理論約束,相信有機酸可於清潔組成物中作為一螯合劑,促進蝕刻後及/或灰化後之殘餘物的移除。
本揭露之清潔組成物選擇性地含有至少一種pH調整劑(例如,一酸或一鹼)以將pH控制於從約7至約12。於某些實施例,本揭露之組成物可具有至少約7(例如,至少約7.5,至少約8,或至少約8.5)至至多約12(例如,至多約11.5,至多約11,至多約10.5,至多約10,至多約9.5,至多約9)之一pH。不欲受理論約束,相信具有高於12之pH的一清潔組成物將電漿蝕刻殘餘物的清潔減至用於完全清潔之一不實際程度,且低於7之pH會將某些金屬或介電材料之蝕刻速率增至一非所欲程度。有效之pH會依用於此處述之清潔組成物中之成份的型式及量而改變。
若有的話,所需pH調整劑的量會改變,因為其它組份的濃度於不同調配物中係不同,特別是羥基胺及有機酸,且係使用之特定pH調整劑之分子量的函數。一般,pH調整劑濃度範圍係清潔組成物之從約0.1%至約3重量%。於某些實施例,本揭露之清潔組成物包括至少約0.1重量%(例如,至少約0.5重量%,至少約1重量%,或至少約1.5重量%)及/或至多約3重量%(例如,至多約2.5重量%,至多約2重量%,或至多約1.5重量%)之pH調整劑。
一般,pH調整劑係無任何金屬離子(除了一微量之金屬離子雜質)。適合之無金屬離子的pH調整劑包括氫氧化銨、四級銨氫氧化物、單胺(包括烷醇胺)、亞胺(諸如,1,8-二氮雜二環[5.4.0]-7-十一烯(DBU)及1,5-二氮雜二環[4.3.0]-5-壬烯(DBN)),及胍鹽(諸如,胍碳酸鹽)。
適合之四級銨氫氧化物的例子不受限地包括氫氧化四甲銨、氫氧化四乙銨、氫氧化四丙銨、氫氧化四丁銨、氫氧化二甲基二乙基銨、膽鹼、氫氧化四乙醇銨、氫氧化苯甲基三甲基銨、氫氧化苯甲基三乙基銨,及氫氧化苯甲基三丁基銨。
適合之單胺的例子不受限地包括三乙胺、三丁胺、三戊胺、乙醇胺、二乙醇胺、二乙胺、丁胺、二丁胺,及苯甲胺。
此外,於某些實施例,本揭露之清潔組成物可含有諸如額外之pH調整劑、腐蝕抑制劑(例如,一經取代或未經取代之苯并三唑)、界面活性劑、額外之有機溶劑、殺生物劑,及消泡劑之添加劑作為選擇性之組份。
適合之消泡劑的例子包括聚矽氧烷消泡劑(例如,聚二甲基矽氧烷)、聚乙二醇甲醚聚合物、環氧乙烷/環氧丙烷之共聚物,及經縮水甘油醚封端之乙炔二醇乙氧化物(諸如,於美國專利第6,717,019號案中所述者,此案在此被併入以供參考)。
於某些實施例,若有多於一種,本揭露之清潔組成物可特別排除呈任何組合之添加劑的一或多種。此等被排除之組份係選自由聚合物、氧清除劑、四級銨氫氧化物、胺、鹼金屬及鹼土金屬之鹼(諸如,NaOH、KOH、LiOH、氫氧化鎂,及氫氧化鈣)、界面活性劑、消泡劑以外者、含氟之化合物、氧化劑(例如,過氧化物、過氧化氫、硝酸鐵、碘酸鉀、過錳酸鉀、硝酸、氯化銨、氯酸銨、碘酸銨、過硼酸銨、過氯酸銨、過碘酸銨、過硫酸銨、氯化四甲銨、氯酸四甲銨、碘酸四甲銨、過硼酸四甲銨、過氯酸四甲銨、過碘酸四甲銨、過硫酸四甲銨、尿素過氧化氫,及過乙酸)、研磨劑(例如,研磨顆粒)、矽酸鹽、羥基羧酸、羧酸及聚羧酸(例如,缺乏胺基基團者)、非唑之腐蝕抑制劑、緩衝劑、胍、胍鹽、無機酸(例如,磺酸、硫酸、亞硫酸、亞硝酸、硝酸、磷酸、亞磷酸,及磷酸)、吡咯烷酮、聚乙烯基吡咯烷酮、金屬鹵化物、具有化學式Wz
MXy
之金屬鹵化物,其中,W係選自H、一鹼金屬或鹼土金屬,及一無金屬離子之氫氧化物鹼部份;M係選自由Si、Ge、Sn、Pt、P、B、Au、Ir、Os、Cr、Ti、Zr、Rh、Ru及Sb所組成群組之一金屬;y係從4至6;且z係1、2,或3,及除本揭露中所述者以外之腐蝕抑制劑所組成之群組。
於某些實施例,本揭露之清潔組成物並非特別設計為自半導體基材移除主體光阻劑膜。相反地,本揭露之清潔組成物可設計為在藉由乾式或濕式剝除方法移除主體阻劑之後移除所有殘餘物。因此,於某些實施例,本揭露之清潔方法較佳係於一乾式或濕式光阻劑剝除方法之後使用。此光阻劑剝除方法一般係藉由一圖案轉移方法進行,諸如,一蝕刻或移植方法,或於圖案轉移之前進行以更正遮罩誤差。殘餘物之化學成分會依進行清潔步驟之一或多種方法而定。
任何適合之乾式剝除方法可用以自半導體基材移除主體阻劑。適合之乾式剝除方法的例子包括以氧為主之電漿灰化,諸如,一氟/氧電漿或一N2
/H2
電漿、臭氧氣相處理、氟電漿處理、熱H2
氣處理(諸如,於美國專利第5,691,117號案中所述者,此案在此被完整併入以供參考)等。此外,熟習此項技藝者所知的任何適合傳統有機濕式剝除溶液可被用以自半導體基材移除主體阻劑。
與本揭露之清潔方法組合使用的一較佳剝除方法係一乾式剝除方法。較佳地,此乾式剝除方法係一以氧為主之電漿灰化方法。此一方法係藉由於一升高溫度(典型上係250°C),於真空條件(即,1托耳)施用一反應性氧氛圍而自半導體基材移除大部份光阻劑。有機材料係藉由此方法氧化,且以處理氣體移除。但是,此方法並未自半導體基材移除無機或有機金屬污染。一其後之以本揭露之清潔組成物清潔此半導體基材對於移除此等殘餘物典型上係必要的。
於某些實施例,本揭露特徵係自一半導體基材清潔殘餘物之方法。此等方法可,例如,藉由將含有蝕刻後殘餘物及/或灰化後殘餘物之一半導體基材與此處所述之一清潔組成物接觸而實施。此方法可進一步包括於接觸步驟後以一沖洗溶劑沖洗半導體基材,及/或於沖洗步驟之後將半導體基材乾燥。於某些實施例,半導體基材可進一步包括一材料(例如,一露出之材料)或一層此材料,其中,此材料係選自由Cu、Co、W、AlOx、AlN、AlOxNy、Ti、TiN、Ta、TaN、TiOx、ZrOx、HfOx,及TaOx所組成之群組。
於某些實施例,清潔方法包括以下步驟: (A)提供一半導體基材,其含有蝕刻後及/或灰化後之殘餘物; (B)將該半導體基材與此處所述之一清潔組成物接觸; (C)以一適合沖洗溶劑沖洗該半導體基材;及 (D)選擇性地,藉由移除沖洗溶劑且不折衷該半導體基材之完整性的任何手段將該半導體基材乾燥。 於某些實施例,清潔方法進一步包括自藉由上述方法獲得之半導體基材形成一半導體裝置(例如,一積體電路,諸如,一半導體晶片)。
欲以此方法清潔之半導體基材可含有有機及有機金屬殘餘物,及另外之一範圍的需被移除的金屬氧化物。半導體基材典型上係由矽、矽鍺、如GaAs之III-V族化合物,或此等之任何組合所構成。半導體基材可另外含有露出之積體電路結構,諸如,互連特徵(例如,金屬線及介電材料)。用於互連特徵之金屬及金屬合金不受限地包括鋁、鋁銅合金、銅、鈦、鉭、鈷、矽、氮化鈦、氮化鉭、鎢,及此等之合金。該半導體基材亦可含有層間介電物、氧化矽、氮化矽、碳化矽、氧化鈦,及以碳摻雜之氧化矽的層狀物。
半導體基材可藉由任何適合方法與一清潔組成物接觸,諸如,將清潔組成物置於一槽內及將半導體基材浸泡及淹沒於清潔組成物內,將清潔組成物噴灑至半導體基材上,將清潔組成物流至半導體基材上,或此等之任何組合。較佳地,半導體基材被浸泡於清潔組成物內。
本揭露之清潔組成物可於最高達約90°C(例如,從約25°C至約80°C,從約30°C至約60°C,或從約40°C至約60°C)的一溫度有效地使用。
相似地,清潔時間可依使用之特別清潔方法及溫度而止於一廣範圍改變。當以一浸泡批次型式方法清潔時,一適合時間範圍係,例如,最高達約60分鐘(例如,從約1分鐘至約60分鐘,從約3分鐘至約20分鐘,或從約4分鐘至約15分鐘)。
用於一單晶圓方法之清潔時間範圍可為從約10秒鐘至約5分鐘(例如,從約15秒鐘至約4分鐘,從約15秒鐘至約3分鐘,或從約20秒鐘至約2分鐘)。
為進一步增強本揭露之清潔組成物的清潔能力,機械式攪拌手段可被使用。適合攪拌手段之例子包括將清潔組成物於基材上循環,將清潔組成物流至或噴灑於基材上,及於清潔處理期間超音波或兆聲波攪拌。半導體基材相對於地面的方向可為任何角度。水平或垂直方向係較佳。
本揭露之清潔組成物可用於熟習此項技藝者所知之傳統清潔工具。本揭露之組成物的一顯著優點係其等全部或部份包括相對較不具毒性、非腐蝕性,及非反應性之組份,因此,組成物於一廣範圍之溫度及處理時間係安定。本揭露之組成物係與用以建構用於批式及單晶圓清潔之現存及提議的半導體晶圓清潔方法的實際上所有材料係化學上可相容。
於清潔之後,半導體基材可以一適合沖洗溶劑沖洗持續約5秒鐘至最高達約5分鐘,其可使用或不使用攪拌手段。適合沖洗溶劑的例子不受限地包括去離子(DI)水、甲醇、乙醇、異丙醇、N-甲基吡咯烷酮、γ-丁內酯、二甲基亞碸、乳酸乙酯,及丙二醇單甲醚乙酸酯。另外,具有pH>8之水性沖洗(諸如,稀的含水氫氧化銨)可被使用。沖洗溶劑之較佳例子不受限地包括稀的含水氫氧化銨、去離子水、甲醇、乙醇,及異丙醇。溶劑可使用與用於施用此處所述之一清潔組成物者相似的手段施用。清潔組成物可於沖洗步驟開始前已自半導體基材移除,或其可於沖洗步驟開始時仍與半導體基材接觸。較佳地,沖洗步驟使用之溫度係於16°C與27°C之間。
選擇性地,半導體基材於沖洗步驟後被乾燥。此項技藝所知之任何適合乾燥手段可被使用。適合乾燥手段之例子包括旋乾式乾燥、將一乾燥氣體流過半導體基材上,以諸如一加熱板或紅外線燈之一加熱裝置加熱半導體基材,馬蘭葛尼(Marangoni)乾燥,羅塔葛尼(Rotagoni)乾燥,IPA乾燥,或此等之任何組合。乾燥時間會依使用之特別方法而定,但典型上係於30秒鐘至最高達數分鐘之等級。
於某些實施例,一種使用此處所述之一清潔組成物製造一積體裝置之方法可包括下列步驟。首先,一層光阻劑被施用至一半導體基材。因而獲得之半導體基材然後可進行一圖案轉移處理,諸如,一蝕刻或移植處理,形成一積體電路。然後,光阻劑之主體可藉由一乾式或濕式剝除方法(例如,一以氧為主之電漿灰化方法)移除。然後,於半導體基材上之留下殘餘物可使用此處所述之一清潔組成物以上述方式移除。半導體基材期後可被處理於基材上形成一或更多個額外電路,或可藉由,例如,組合(例如,切片及結合)及封裝(例如,晶片密封)處理形成一半導體晶片。
此處引述之所有公開文獻(例如,專利案、專利申請公開案,及文件)之內容在此被完整併入以供參考。 範例
本揭露參考下列範例作更詳細說明,此等範例係用於說明目的且不應作為限制本揭露之範圍而作解釋。除非作其它特定,列示之任何百分率係以重量(重量%)。除非作其它特定,列示之所有蝕刻速率係平均蝕刻速率。除非作其它表示,測試期間之控制式攪拌係以一1英吋攪拌棒以300 rpm進行。 一般程序 調配摻合
本揭露之組成物係藉由將有機溶劑及超純去離子水(DIW)濕合同時攪拌而製備。達成一均勻溶液之後,添加剩餘組份。使用之所有組份係可購得且具高純度。 一般程序2 以燒杯測試之清潔評估
自一基材清潔PER(蝕刻後之殘餘物)係以上述清潔組成物使用含有Co/TiN/Ti/TiOx/ILD之一多層式基材進行。
測試片係使用4”長之塑膠鎖合鉗固定,藉此,測試片其後可被懸浮於含有約200毫升之本揭露的一清潔組成物之一500毫升體積之玻璃燒杯內。於將測試片浸泡於清潔組成物內之前,組成物被預熱至所欲測試條件溫度(典型上係如所示之40°C或65°C)並且控制式攪拌。然後,清潔測試係藉由將以塑膠鉗固定之測試片以使測試片的含有PER層之側面向攪拌棒之方式置於經加熱之組成物內而進行。將測試片靜置於清潔組成物內持續一段時間(典型上係5至15分鐘),同時使組成物於控制式攪拌下維持於測試溫度。當所欲清潔時間完成時,測試片自清潔組成物快速移除且置於以於環境溫度(~17°C)之約400毫升去離子水填充之一500毫升pyrex燒杯內,並且溫和攪拌。測試片留於去離子水之燒杯內持續約6秒鐘,然後快速移除,並且移至含有一相似量的IPA之一玻璃燒杯,以供溫和攪拌約30秒鐘。測試片立即曝露於來自一手持式吹氮氣槍之一氮氣流,此造成測試片上之任何滴液自測試片吹掉,且進一步使測試片裝置表面完全乾燥。於此最終氮氣乾燥步骤之後,測試片自塑膠鉗固定器移除,並且置於一覆蓋式塑膠載體內且裝置側向上,持續不大於約2小時之短期貯存。然後,經清潔之測試片裝置表面的主要特徵之掃瞄式電子顯微術(SEM)影像被收集。 一般程序3 以燒杯測試之材料相容性評估
於矽基材(即,矽晶圓)上之Co敷層,於矽基材上之TiOx,於矽基材上之TiN,於矽基材上之AlOx,及/或於矽基材上之W合金被切成約1英吋 x 1英吋之矩形測試片,以供材料相容性測試。測試片被初始測量厚度或片電阻,對於一金屬膜(Co)係藉由4點探針,CDE Resmap 273,或對於一介電膜(TiOx、TiN,或AlOx)係藉由橢圓偏振術,使用一Woollam M-2000X。然後,測試片安裝於4”長塑膠鎖合鉗上,且如一般程序2中之清潔程序中所述般處理(除非作其它特定),且測試片之含有Co、W合金、TiOx、TiN,或AlOx層之側係面向攪拌棒,持續10分鐘。
於最終氮氣乾燥步驟之後,測試片自塑膠鉗固定器移除,且置於一覆蓋式塑膠載體內。然後,後厚度(post thickness)或片電阻係於後處理之測試片表面上收集,對於一金屬膜(Co或W合金)係藉由4點探針,CDE Resmap 273,或對於介電膜(TiOx、TiN,或AlOx)係藉由橢圓偏振術,使用一Woollam M-2000X。 調配例FE-1至FE-6
清潔調配物FE-1至FE-6(所有皆含有一含硫之添加劑及一含金屬之添加劑)係藉由一般程序1製備。其等之組成係綜述於表1中。 表1
DEGBE=二乙二醇丁醚;Hex glycol=己二醇;MSA=甲磺酸;DTPA=二伸乙路基三胺五乙酸;5MBTA=5-甲基苯并三唑;DBU=1,8-二氮雜二環[5.4.0]十一-7-烯 範例1-6 清潔劑與露出鈷之相容性
調配物FE-1至FE-6係依據一般程序2,使用一經圖案化之矽基材,其含有位於一露出鈦層下之一鈷層,測試鈷腐蝕抑能力。露出鈷藉由清潔組成物之損失(即,藉由清潔組成物移除之露出鈷的數量)被測量並且顯示於表2中。 表2
表2中之數據顯示驚人地,當用於清潔於一經圖案化之矽基材上的蝕刻後殘餘物時,調配物FE-4及FE-5(其等含有具化學式(I)之一環狀胺)展現極低或無鈷腐蝕作用。調配物FE-1(其不含有胺)、FE-2(其含有一三級胺),及FE-3(其含有與具有化學式(1)者不同之一環狀胺)展現比調配物FE-1更高量之鈷腐蝕作用。
此外,FE-4及FE-6具有相同pH,但含有不同鹼性化合物。結果顯示FE-4(其含有具化學式(I)之一環狀胺)展現比FE-6(其含有氫氧化銨,而非具有化學式(I)之一環狀胺)顯著更佳之鈷腐蝕抑制。此等結果暗示具化學式(I)之環狀胺促進FE-4之較佳鈷腐蝕抑制效果。 調配例FE-7至FE-12
清潔調配物FE-7至FE-12(所有皆含有一含硫之添加劑及一含金屬之添加劑)係藉由一般程序1製備。其等之組成係綜述於表3中。特別地,調配物FE-7至FE-12含有一增加量之DBU。 表3
範例7-12 清潔劑與露出之金屬或介電質的相容性
調配物FE-7至FE-12係依據一般程序2,使用含有露出之鈷的一經圖案化之矽基材測試材料相容性。調配物FE-7至FE-9、FE-11,及FE-12係依據一般程序3,使用於矽基材上之覆膜,於65o
C測試材料相容性持續4分鐘。經圖案化之矽基材上藉由清潔組成物之露出鈷的損失(即,藉由清潔組成物移除之露出鈷的數量)被測量且顯示於表4中。作為矽基材上之覆膜的W合金、Co、AlOx、TiOx,及TiN之藉由清潔調配物的蝕刻速率(ER)(埃/分鐘)係顯示於表5中。 表4
表5
-經W合金塗覆之晶圓浸泡於清潔調配物中持續20分鐘,同時此等調配物以250 rpm攪拌。然後,此等晶圓以異丙醇沖洗15秒鐘兩次,及以去離子水沖洗1分鐘。 -其它晶圓浸泡於清潔調配物中持續10分鐘,同時此等調配物以250 rpm攪拌。然後,此等晶圓以異丙醇沖洗15秒鐘兩次,及以去離子水沖洗15秒鐘。
表4中之數據顯示清潔調配物FE-7至FE-12於一經圖案化之矽基材皆展現明顯降低或實質上無鈷損失或蝕刻。表5中之數據顯示清潔調配物FE-7至FE-9、FE-11,及FE-12一般展現作為矽基材上之覆膜的金屬或介電物(諸如,W合金、Co、AlOx、TiOx,及TiN)之一或多者的降低腐蝕或蝕刻。 調配例FE-13至FE-16
清潔調配物FE-13至FE-16(此等皆含有一胺基酸添加劑及一含金屬之添加劑)係藉由一般程序1製備。其等之組成係綜述於6中。特別地,調配物FE-13至FE-16具有實質上相同組成,除了甲磺酸(MSA)之量及因而之pH外。 表 6
範例13-16 清潔劑與露出之金屬的相容性
調配物FE-13至FE-16係依據一般程序3,使用於矽基材上之覆膜,於65o
C測試材料目容性持續4分鐘。W合金、Co、AlOx、TiOx,及TiN藉由清潔調配物之蝕刻速率(ER)(埃/分鐘)係顯示於表7中。 表7
表7中之數據顯示當清潔調配物之pH值於9與12之間時,清潔調配物FE-13至FE-15一般展現作為矽基材上之覆膜的金屬或介電質(諸如,W合金、Co、AlOx、TiOx,及TiN)之一或多者的降低腐蝕或蝕刻。調配物FE-16展現比FE-13至FE-15更高程度之金屬或介電質的腐蝕,其至少部份係由於其較高pH(即,>12)之故。 調配例FE-17至FE-18
清潔調配物FE-17至FE-18(其等皆含有一含硫之添加劑及一含金屬之添加劑)係藉由一般程序1製備。其等之組成係綜述於表8中。 表8
DBU=1,8-二氮雜二環[5.4.0]十一-7-烯;DBN=1,5-二氮雜二環[4.3.0]-5-壬烯 範例17-18 清潔劑與露出之金屬的相容性
表9中之數據顯示調配物FE-17及FE-18(二者皆含有具化學式(I)之環狀胺)展現於矽基材上之露出鈷的低腐蝕或蝕刻。換言之,此結果暗示如同DBU,DBN亦展現於一矽基材上明顯降低之鈷腐蝕或蝕刻。
雖然本揭露已參考其某些實施例作詳細說明,但需瞭解修改及改變係於所述及請求者之精神及範圍內。
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Claims (39)
- 一種清潔組成物,其包含:1)至少一氧化還原劑,該至少一氧化還原劑包含羥基胺; 2)至少一水溶性有機溶劑;3)該組成物從約0.001重量%至約0.5重量%之量的至少一含金屬之添加劑;4)至少一環狀胺;及5)水。
- 一種清潔組成物,其包含:1)至少一氧化還原劑;2)至少一水溶性有機溶劑;3)該組成物從約0.001重量%至約0.5重量%之量的至少一含金屬之添加劑;4)至少一環狀胺;及5)水,其中該至少一含金屬之添加劑包含一2A族金屬、一3B族金屬、一4B族金屬、一5B族金屬,或一鑭系金屬。
- 一種清潔組成物,其包含:1)至少一氧化還原劑;2)至少一水溶性有機溶劑;3)該組成物從約0.001重量%至約0.5重量%之量的至少一含金屬之添加劑;4)至少一環狀胺;5)甘胺酸;及6)水。
- 如請求項1至4中任一項之組成物,其中該組成物具有約7至約12之一pH。
- 如請求項1至4中任一項之組成物,其中該至少一環狀胺係該組成物之從約0.1重量%至約2重量%。
- 如請求項1、3及4中任一項之組成物,其中該至少一氧化還原劑包含羥基胺。
- 如請求項1至4中任一項之組成物,其中該至少一氧化還原劑係該組成物之從約0.5重量%至約20重量%。
- 如請求項1至4中任一項之組成物,其中該至少一水溶性有機溶劑包含二有機溶劑。
- 如請求項12之組成物,其中該等二有機溶劑係每一者獨立地選自由伸烷基二醇及伸烷基二醇醚所組成之群組。
- 如請求項1至4中任一項之組成物,其中該至少一水溶性有機溶劑係該組成物之從約60重量%至約95重量%。
- 如請求項1至4中任一項之組成物,其中該至少一含金屬之添加劑包含一金屬鹵化物、一金屬氫氧化物、一金屬硼化物、一金屬烷氧化物、一金屬氧化物,或一含金屬之銨鹽。
- 如請求項1、2及4中任一項之組成物,其中該至少一含金屬之添加劑包含一2A族金屬、一3B族金屬、一4B族金屬、一5B族金屬,或一鑭系金屬。
- 如請求項3之組成物,其中該至少一含金屬之添加劑包含Ca、Ba、Ti、Hf、Sr、La、Ce、W、V、Nb,或Ta。
- 如請求項16之組成物,其中該至少一含金屬之添加劑包含Ca、Ba、Ti、Hf、Sr、La、Ce、W、V、Nb,或Ta。
- 如請求項1至4中任一項之組成物,其中該至少一含金屬之添加劑包含硼化鎢、Ca(OH)2、BaCl2、SrCl2、LaCl3、CeCl3、(NH4)2TiF6、BaTiO3、Ti(OEt)4、Ti(OCH(CH3)2)4、HfO2、V2O5、Nb2O5,或TaF3。
- 如請求項1至4中任一項之組成物,其中該至少一含金屬之添加劑係該組成物之從約0.001重量%至約0.4重量%。
- 如請求項1至4中任一項之組成物,其中該水係該組成物之從約5重量%至約28重量%。
- 如請求項1至4中任一項之組成物,進一步包含一pH調整劑,該pH調整劑係與該至少一環狀胺不同。
- 如請求項1至3中任一項之組成物,進一步包含至少一清潔添加劑。
- 如請求項23之組成物,其中該至少一清潔添加劑包含一含硫之添加劑。
- 如請求項24之組成物,其中該含硫之添加劑包含一硫醇或一硫醚。
- 如請求項25之組成物,其中該含硫之添加劑包含3-胺基-5-巰基-1H-1,2,4-三唑、β-巰基乙醇、3-胺基-5-甲硫基-1H-1,2,4-三唑、1-苯基-1H-四唑-5-硫醇、4-甲基-4H-1,2,4-三唑-3-硫醇、2-吡啶硫醇,或3-巰基-丙酸。
- 如請求項24之組成物,其中該含硫之 添加劑係該組成物之從約0.01重量%至約0.15重量%。
- 如請求項23之組成物,其中該至少一清潔添加劑包含一有機酸。
- 如請求項28之組成物,其中該有機酸包含一羧酸或一磺酸。
- 如請求項28之組成物,其中該有機酸係該組成物之從約0.1重量%至約0.5重量%。
- 如請求項23之組成物,其中該至少一清潔添加劑包含一胺基酸。
- 如請求項31之組成物,其中該胺基酸係甘胺酸。
- 如請求項31之組成物,其中該胺基酸係該組成物之從約0.01重量%至約0.15重量%。
- 如請求項1至4中任一項之組成物,其中該至少一環狀胺係該組成物之從約0.264重量%至約0.396重量%。
- 一種用於清潔半導體基材之方法,其包含:將含有蝕刻後殘餘物或灰化後殘餘物之一半導體基材與如請求項1至34中任一項之清潔組成物接觸。
- 如請求項35之方法,其中該半導體基材進一步包含一層,該層包含一選自由Cu、Co、W、AlOx、AlN、AlOxNy、Ti、TiN、Ta、TaN、TiOx、ZrOx、HfOx,及TaOx所組成之群組的材料。
- 如請求項35之方法,進一步包含於該接觸步驟後將該半導體基材以一沖洗溶劑沖洗。
- 如請求項37之方法,進一步包含於該沖洗步驟後將該半導體基材乾燥。
- 如請求項35之方法,進一步包含從該半導體基材形成一半導體裝置。
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CN112424327A (zh) * | 2018-07-20 | 2021-02-26 | 恩特格里斯公司 | 含腐蚀抑制剂的清洗组合物 |
CN110767534B (zh) * | 2019-10-28 | 2021-12-28 | 江苏晶杰光电科技有限公司 | 一种晶圆的清洗方法 |
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IL269487A (en) | 2019-11-28 |
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