TW202227602A - 微電子裝置清潔組合物 - Google Patents
微電子裝置清潔組合物 Download PDFInfo
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- TW202227602A TW202227602A TW110136877A TW110136877A TW202227602A TW 202227602 A TW202227602 A TW 202227602A TW 110136877 A TW110136877 A TW 110136877A TW 110136877 A TW110136877 A TW 110136877A TW 202227602 A TW202227602 A TW 202227602A
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- UKLQXHUGTKWPSR-UHFFFAOYSA-M oxyphenonium bromide Chemical compound [Br-].C=1C=CC=CC=1C(O)(C(=O)OCC[N+](C)(CC)CC)C1CCCCC1 UKLQXHUGTKWPSR-UHFFFAOYSA-M 0.000 description 1
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- 229910001950 potassium oxide Inorganic materials 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- KCXFHTAICRTXLI-UHFFFAOYSA-N propane-1-sulfonic acid Chemical compound CCCS(O)(=O)=O KCXFHTAICRTXLI-UHFFFAOYSA-N 0.000 description 1
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- KRIOVPPHQSLHCZ-UHFFFAOYSA-N propiophenone Chemical compound CCC(=O)C1=CC=CC=C1 KRIOVPPHQSLHCZ-UHFFFAOYSA-N 0.000 description 1
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- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 description 1
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- 239000002994 raw material Substances 0.000 description 1
- 229910052702 rhenium Inorganic materials 0.000 description 1
- WUAPFZMCVAUBPE-UHFFFAOYSA-N rhenium atom Chemical compound [Re] WUAPFZMCVAUBPE-UHFFFAOYSA-N 0.000 description 1
- HEBKCHPVOIAQTA-ZXFHETKHSA-N ribitol Chemical compound OC[C@H](O)[C@H](O)[C@H](O)CO HEBKCHPVOIAQTA-ZXFHETKHSA-N 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 238000005201 scrubbing Methods 0.000 description 1
- CDAISMWEOUEBRE-UHFFFAOYSA-N scyllo-inosotol Natural products OC1C(O)C(O)C(O)C(O)C1O CDAISMWEOUEBRE-UHFFFAOYSA-N 0.000 description 1
- 150000003333 secondary alcohols Chemical class 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 1
- 229910010271 silicon carbide Inorganic materials 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- APSBXTVYXVQYAB-UHFFFAOYSA-M sodium docusate Chemical group [Na+].CCCCC(CC)COC(=O)CC(S([O-])(=O)=O)C(=O)OCC(CC)CCCC APSBXTVYXVQYAB-UHFFFAOYSA-M 0.000 description 1
- JXKPEJDQGNYQSM-UHFFFAOYSA-M sodium propionate Chemical compound [Na+].CCC([O-])=O JXKPEJDQGNYQSM-UHFFFAOYSA-M 0.000 description 1
- 239000004324 sodium propionate Substances 0.000 description 1
- 235000010334 sodium propionate Nutrition 0.000 description 1
- 229960003212 sodium propionate Drugs 0.000 description 1
- 239000004328 sodium tetraborate Substances 0.000 description 1
- UELAIMNOXLAYRW-UHFFFAOYSA-M sodium;1,4-dicyclohexyloxy-1,4-dioxobutane-2-sulfonate Chemical compound [Na+].C1CCCCC1OC(=O)C(S(=O)(=O)[O-])CC(=O)OC1CCCCC1 UELAIMNOXLAYRW-UHFFFAOYSA-M 0.000 description 1
- 239000001593 sorbitan monooleate Substances 0.000 description 1
- 235000011069 sorbitan monooleate Nutrition 0.000 description 1
- 229940035049 sorbitan monooleate Drugs 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 229910052682 stishovite Inorganic materials 0.000 description 1
- 150000005846 sugar alcohols Chemical class 0.000 description 1
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 1
- 150000003460 sulfonic acids Chemical class 0.000 description 1
- 229910052715 tantalum Inorganic materials 0.000 description 1
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 description 1
- MZLGASXMSKOWSE-UHFFFAOYSA-N tantalum nitride Chemical compound [Ta]#N MZLGASXMSKOWSE-UHFFFAOYSA-N 0.000 description 1
- 229960001367 tartaric acid Drugs 0.000 description 1
- FBWNMEQMRUMQSO-UHFFFAOYSA-N tergitol NP-9 Polymers CCCCCCCCCC1=CC=C(OCCOCCOCCOCCOCCOCCOCCOCCOCCO)C=C1 FBWNMEQMRUMQSO-UHFFFAOYSA-N 0.000 description 1
- BVQJQTMSTANITJ-UHFFFAOYSA-N tetradecylphosphonic acid Chemical compound CCCCCCCCCCCCCCP(O)(O)=O BVQJQTMSTANITJ-UHFFFAOYSA-N 0.000 description 1
- CBXCPBUEXACCNR-UHFFFAOYSA-N tetraethylammonium Chemical compound CC[N+](CC)(CC)CC CBXCPBUEXACCNR-UHFFFAOYSA-N 0.000 description 1
- ZOMVKCHODRHQEV-UHFFFAOYSA-M tetraethylphosphanium;hydroxide Chemical compound [OH-].CC[P+](CC)(CC)CC ZOMVKCHODRHQEV-UHFFFAOYSA-M 0.000 description 1
- YQIVQBMEBZGFBY-UHFFFAOYSA-M tetraheptylazanium;bromide Chemical compound [Br-].CCCCCCC[N+](CCCCCCC)(CCCCCCC)CCCCCCC YQIVQBMEBZGFBY-UHFFFAOYSA-M 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- BSYVTEYKTMYBMK-UHFFFAOYSA-N tetrahydrofurfuryl alcohol Chemical compound OCC1CCCO1 BSYVTEYKTMYBMK-UHFFFAOYSA-N 0.000 description 1
- ISXOBTBCNRIIQO-UHFFFAOYSA-N tetrahydrothiophene 1-oxide Chemical compound O=S1CCCC1 ISXOBTBCNRIIQO-UHFFFAOYSA-N 0.000 description 1
- AHNISXOXSNAHBZ-UHFFFAOYSA-M tetrakis-decylazanium;bromide Chemical compound [Br-].CCCCCCCCCC[N+](CCCCCCCCCC)(CCCCCCCCCC)CCCCCCCCCC AHNISXOXSNAHBZ-UHFFFAOYSA-M 0.000 description 1
- OKIZCWYLBDKLSU-UHFFFAOYSA-N tetramethylazanium;hydrochloride Chemical compound Cl.C[N+](C)(C)C OKIZCWYLBDKLSU-UHFFFAOYSA-N 0.000 description 1
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 1
- CRUVUWATNULHFA-UHFFFAOYSA-M tetramethylphosphanium;hydroxide Chemical compound [OH-].C[P+](C)(C)C CRUVUWATNULHFA-UHFFFAOYSA-M 0.000 description 1
- OORMKVJAUGZYKP-UHFFFAOYSA-M tetrapropylphosphanium;hydroxide Chemical compound [OH-].CCC[P+](CCC)(CCC)CCC OORMKVJAUGZYKP-UHFFFAOYSA-M 0.000 description 1
- 229940113082 thymine Drugs 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 229910052905 tridymite Inorganic materials 0.000 description 1
- JLGLQAWTXXGVEM-UHFFFAOYSA-N triethylene glycol monomethyl ether Chemical compound COCCOCCOCCO JLGLQAWTXXGVEM-UHFFFAOYSA-N 0.000 description 1
- ITMCEJHCFYSIIV-UHFFFAOYSA-M triflate Chemical compound [O-]S(=O)(=O)C(F)(F)F ITMCEJHCFYSIIV-UHFFFAOYSA-M 0.000 description 1
- RRHXZLALVWBDKH-UHFFFAOYSA-M trimethyl-[2-(2-methylprop-2-enoyloxy)ethyl]azanium;chloride Chemical compound [Cl-].CC(=C)C(=O)OCC[N+](C)(C)C RRHXZLALVWBDKH-UHFFFAOYSA-M 0.000 description 1
- 150000004072 triols Chemical class 0.000 description 1
- BSVBQGMMJUBVOD-UHFFFAOYSA-N trisodium borate Chemical compound [Na+].[Na+].[Na+].[O-]B([O-])[O-] BSVBQGMMJUBVOD-UHFFFAOYSA-N 0.000 description 1
- 238000011144 upstream manufacturing Methods 0.000 description 1
- 229940035893 uracil Drugs 0.000 description 1
- 150000003672 ureas Chemical class 0.000 description 1
- 239000012808 vapor phase Substances 0.000 description 1
- 229920003169 water-soluble polymer Polymers 0.000 description 1
- 238000004876 x-ray fluorescence Methods 0.000 description 1
Classifications
-
- 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
- C11D7/00—Compositions of detergents based essentially on non-surface-active compounds
- C11D7/22—Organic compounds
- C11D7/32—Organic compounds containing nitrogen
- C11D7/3218—Alkanolamines or alkanolimines
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/16—Organic compounds
- C11D3/20—Organic compounds containing oxygen
- C11D3/2075—Carboxylic acids-salts thereof
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/16—Organic compounds
- C11D3/26—Organic compounds containing nitrogen
- C11D3/28—Heterocyclic compounds containing nitrogen in the ring
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/16—Organic compounds
- C11D3/26—Organic compounds containing nitrogen
- C11D3/32—Amides; Substituted amides
- C11D3/323—Amides; Substituted amides urea or derivatives thereof
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/16—Organic compounds
- C11D3/26—Organic compounds containing nitrogen
- C11D3/33—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
- C11D3/36—Organic compounds containing phosphorus
- C11D3/361—Phosphonates, phosphinates or phosphonites
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D7/00—Compositions of detergents based essentially on non-surface-active compounds
- C11D7/22—Organic compounds
- C11D7/36—Organic compounds containing 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
- C11D7/00—Compositions of detergents based essentially on non-surface-active compounds
- C11D7/50—Solvents
- C11D7/5004—Organic solvents
- C11D7/5022—Organic solvents containing oxygen
-
- 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
- H01L21/02041—Cleaning
- H01L21/02057—Cleaning during device manufacture
-
- 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
- H01L21/02041—Cleaning
- H01L21/02057—Cleaning during device manufacture
- H01L21/0206—Cleaning during device manufacture during, before or after processing of insulating layers
- H01L21/02065—Cleaning during device manufacture during, before or after processing of insulating layers the processing being a planarization of insulating layers
-
- 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
- H01L21/02041—Cleaning
- H01L21/02057—Cleaning during device manufacture
- H01L21/02068—Cleaning during device manufacture during, before or after processing of conductive layers, e.g. polysilicon or amorphous silicon layers
-
- 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
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Wood Science & Technology (AREA)
- Life Sciences & Earth Sciences (AREA)
- Organic Chemistry (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- Power Engineering (AREA)
- General Physics & Mathematics (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Computer Hardware Design (AREA)
- Physics & Mathematics (AREA)
- Manufacturing & Machinery (AREA)
- Health & Medical Sciences (AREA)
- Emergency Medicine (AREA)
- Detergent Compositions (AREA)
- Cleaning Or Drying Semiconductors (AREA)
Abstract
本發明提供一種用於清潔微電子裝置基板之組合物。該組合物可用於清潔具有暴露之鈷、鉬、銅、鉬、鎢及介電質表面之製程內微電子裝置基板。亦提供一種清潔此等裝置之方法及包含該組合物之組分中之一或多者之套組。
Description
本發明大體上係關於水性組合物,其用於清潔微電子裝置基板之表面,諸如用於清潔來自微電子裝置基板表面之殘留物。
微電子裝置基板係用於製備積體電路裝置。微電子裝置基板包含基底,諸如具有高度平坦表面之矽晶圓。經由多次選擇性放置及移除步驟,將電子功能特徵之區域添加至基底之平坦表面上。該等特徵藉由選擇性添加及移除會展示絕緣、導電或半導電性質之電子功能材料製成。此等電子功能材料藉由使用包含光阻劑、化學蝕刻劑之加工材料及含有磨料粒子及幫助加工表面之化學材料之漿液按所需放置。
積體電路之一個特徵為導電「互連」陣列,其亦稱作「線」及「通路」。作為積體電路之部分,導電互連功能為在各種其他電子特徵中及之間傳導電流。各互連係以導電材料之線或薄膜形式,該導電材料在絕緣材料(即,介電材料,諸如介電材料)中形成之開口內延伸且係藉由該開口定義(在形狀及大小上)。介電材料充當極其緊密間隔之互連結構之間及互連結構與積體電路之其他電子特徵之間之絕緣體。
必須選擇用於產生互連及介電結構之材料之類型以適當用作以高效率及高可靠性表現之積體電路之一部分。例如,互連之導電材料應為在材料之間存在電壓下隨時間且在使用期間不過度遷移(例如,擴散)至相鄰介電材料之類型;互連材料至相鄰介電材料之此遷移通常被稱作「電遷移」。同時,組合之互連及介電材料結構必須具有足夠完整性,包含在此等材料之間之介面,以導致低程度之缺陷及高程度之性能可靠性。例如,強結合必須在介面處存在以防止在使用期間介電材料與互連材料分離。
互連過去通常由鋁或鎢製成,及最近由銅製成。銅相對於鋁及鎢具有有利高的導電性。此外,銅基互連如與鋁相比提供對電遷移之更佳抗性,從而提高積體電路隨時間之可靠性。然而,銅離子可傾向於在足夠電偏壓下擴散至二氧化矽(SiO
2),且銅與二氧化矽及其他介電材料之黏附可係差的。
為防止銅與介電材料之此等負相互作用,最近積體電路結構已經設計以包含銅互連結構與相鄰介電材料之間之障壁層。實例障壁層可為導電材料或非導電材料,實例包括鉭(Ta)、氮化鉭(TaN
x)、鎢(W)、鈦(Ti)、氮化鈦(TiN)、釕(Ru)、鈷(Co)、鉬(Mo)、錸(Rh)及其合金。
將微電子裝置之各種特徵放在基板上之方法包括將絕緣材料(例如,介電質等)、半導體材料、金屬材料(例如,導電線及通路(即,互連)等選擇性放在基板表面上。此等材料之選擇性放置及移除可涉及於諸如光阻劑塗覆、蝕刻(例如,濕法蝕刻、電漿蝕刻)、化學-機械加工(亦稱作化學-機械研磨、化學-機械平坦化或簡稱作「CMP」)及灰化(「電漿灰化」)之步驟中使用加工組合物,諸如尤其光阻劑、蝕刻劑、含有磨料及化學材料之CMP漿液及電漿。
化學-機械加工為一種製程,藉由該製程將其極少量(厚度)之材料自微電子裝置基板表面精確移除以研磨(或「平坦化」)該表面,從而準備後續材料層待施覆至經加工表面。化學-機械加工涉及表面之高度精確機械研磨,聯合化學材料之可控相互作用(諸如存在於表面或自表面移除之材料之氧化、還原或螯合)。通常,以高選擇性優先移除基板表面上之一種類型之材料(例如,金屬超載荷),與亦存在於該表面處之一或多種其他材料(例如,介電材料)之減少移除程度相比。
CMP製程涉及將「漿液」施覆至表面連同使該表面與正在移動之CMP墊接觸。「漿液」為液體組合物,其含有提供表面之機械研磨之微磨料粒子,連同與表面之材料化學相互作用以促進某種材料自表面選擇性移除且通常抑制另一表面材料之移除之化學材料。將漿液施覆至表面,同時CMP墊以所需量之壓力及移動與該表面接觸以促進研磨所選材料及自該表面化學移除。墊之機械作用及磨料粒子抵靠表面移動,連同化學成分之作用之組合達成表面之具有所需低水平之缺陷及殘留物的所需移除、平坦化及研磨。該CMP製程應產生高度平面、低缺陷、低殘留物表面,可向該表面施覆微電子裝置之後續層。
於加工步驟(例如,化學-機械加工、蝕刻、灰化等)後,至少一定量之殘留物將存在於基板表面處。殘留物可包含來自CMP漿液之磨料粒子或其他加工材料;為CMP漿液之一部分之活性化學成分(例如,氧化劑、觸媒、抑制劑)或其他加工組合物(例如,蝕刻劑);加工材料或其成分之反應產物或副產物;化學蝕刻劑;光阻劑聚合物或其他固體加工成分等。任何此殘留物必須在進行微電子裝置製造製程之後續步驟之前藉由清潔表面來移除,以避免缺陷或降低裝置性能或可靠性之其他潛在來源。
於(例如)於蝕刻步驟後,於CMP步驟後,或用於製造多層微電子裝置之另一步驟後通常用於清潔微電子基板表面之某些方法及設備包括涉及清潔溶液在表面上方之流動與超高頻音波、噴射或刷洗組合以移除殘留物及污染物之彼等。典型清潔溶液為鹼性溶液,例如,含有適宜氫氧化物化合物連同其他化學材料,該等其他化學材料一起藉由與殘留物化學相互作用將殘留物自表面移除。清潔溶液不僅應自表面有效移除高百分比之殘留物,而且必須關於基板之功能特徵為安全。清潔溶液必須不引起對彼等特徵之損害。例如,清潔溶液應不引起對基板之金屬特徵之腐蝕(即,氧化),例如,不應氧化可作為互連或障壁特徵存在之基板之銅或鈷金屬特徵。
不斷尋求新穎可用且改良之清潔組合物及特定成分,尤其併與新穎微電子裝置結構,諸如現可包含鎢、銅、鈷、鉬及介電材料之暴露表面之彼等結構使用。
存在對於自製程內微電子裝置基板表面移除殘留物方面有效之組合物及方法之持續需求。本發明提供此等組合物及方法,同時亦抑制對某些金屬特徵,諸如鈷、銅、鉬及鎢,以及介電質表面介電材料,包括(但不限於)二氧化矽、氮化矽、碳化矽、氧氮化矽、氧碳化矽、矽、碳、介電質(諸如SiLK™介電質(Dow Chemical))、倍半矽氧烷或Black Diamond® PECVD (Applied Materials)之損害(即,腐蝕),其等可在微電子裝置上以暴露特徵存在。
於一個態樣中,本發明提供組合物,其包含:
a.水;
b.錯合劑;及
c.胺基(C
6-C
12烷基)醇;
其中該組合物不含選自含胍官能基化合物、含吡唑酮官能基化合物或羥基喹啉化合物之腐蝕抑制劑。
亦提供一種使用此等組合物清潔微電子裝置基板之方法及包含該等組合物之一或多種組分於一或多個容器中之套組。
於第一態樣中,本發明提供組合物,其包含:
a.水;
b.錯合劑;及
c.胺基(C
6-C
12烷基)醇;
其中該組合物不含選自含胍官能基化合物、含吡唑酮官能基化合物或羥基喹啉化合物之腐蝕抑制劑。
於一個實施例中,該組合物包含約60至90重量%水,約0.01至約10重量%錯合劑,及約0.1至約5重量%,或約0.1至約2重量%胺基(C
6-C
12烷基)醇。
於一個實施例中,該組合物由以上組分a.至c.組成或基本上由其組成。
如本文中所用,除非另有指定,否則描述為「基本上由一或多個指定條項組成」之組合物或組合物之成分係指僅由彼等指定條項與不超過無實質量之其他(另外)材料組成,例如,基於組合物或成分之總重量計,僅含有指定條項且不超過5、3、2、1、0.5、0.1、0.05或0.01重量%另外成分之組合物或成分。如本文中所用,描述為「由一或多個指定條項組成」之組合物或組合物之成分係指僅由彼等指定條項組成之組合物或成分。
於某些實施例中,pH將為酸性,例如,約1.5至約6及於其他實施例中,pH將為鹼性,例如,約9至約14。一般技術者將知曉適用於此目的之彼等酸及鹼。
於一個實施例中,pH調節劑為鹼。出於此目的之pH調節劑之非限制性實例包括:氫氧化膽鹼、四丁基氫氧化鏻(TBPH)、四甲基氫氧化鏻、四乙基氫氧化鏻、四丙基氫氧化鏻、苄基三苯基氫氧化鏻、甲基三苯基氫氧化鏻、乙基三苯基氫氧化鏻、N-丙基三苯基氫氧化鏻、四乙基氫氧化銨(TEAH)、四丙基氫氧化銨(TPAH)、四丁基氫氧化銨(TBAH)、三甲基乙基氫氧化銨、二乙基二甲基氫氧化銨、三丁基甲基氫氧化銨(TBMAH)、苄基三甲基氫氧化銨(BTMAH)、四甲基銨鹽酸鹽(TMAC)、參(2-羥乙基)甲基氫氧化銨、二乙基二甲基氫氧化銨、精胺酸、氫氧化鉀、氫氧化銫及其組合。
於一個實施例中,該pH調節劑係選自氫氧化膽鹼及四乙基氫氧化銨(TEAH)。
於另一實施例中,該pH調節劑為酸,且可選自硝酸、檸檬酸、硫酸、磷酸、鹽酸、氫溴酸、甲磺酸、苯磺酸及對甲苯磺酸、三氟甲磺酸、乙酸、乳酸、乙醇酸或其任何組合。
於一個實施例中,該錯合劑係選自:胺、胺基酸及季胺化胺基酸,包括(但不限於) 4-(2-羥乙基)嗎啉(HEM)、1,2-環己二胺-N,N,N',N'-四乙酸(CDTA)、羥乙基乙二胺三乙酸(HEDTA)、乙二胺四乙酸(EDTA)、間苯二甲胺(MXDA)、亞胺基二乙酸(IDA)、三甲胺、異丙醇胺、二異丙醇胺、哌嗪、羥乙基哌嗪、二羥基乙基哌嗪、葡糖胺、N-甲基葡糖胺、2-(羥乙基)亞胺基二乙酸(HIDA)、氮基三乙酸、硫脲、1,1,3,3-四甲基脲、脲、脲衍生物、尿酸、丙胺酸、精胺酸、天冬醯胺、天冬胺酸、半胱胺酸、麩胺酸、麩胺醯胺、組胺酸、異白胺酸、白胺酸、離胺酸、甲硫胺酸、苯丙胺酸、脯胺酸、絲胺酸、蘇胺酸、色胺酸、酪胺酸、纈胺酸、牛磺酸、甜菜鹼及其組合。
或者,或除了以上提及之錯合劑外,另外錯合劑可包括膦酸鹽(例如,1-羥基亞乙基-1,1-二膦酸(HEDP)、1,5,9-三氮雜環十二烷-N,N',N''-參(亞甲基膦酸) (DOTRP)、1,4,7,10-四氮雜環十二烷-N,N',N'',N'''-肆(亞甲基膦酸) (DOTP)、氮基參(亞甲基)三膦酸、二伸乙基三胺五(亞甲基膦酸) (DETAP)、胺基三(亞甲基膦酸)、雙(六亞甲基)三胺五亞甲基膦酸、1,4,7-三氮雜環壬烷-N,N',N''-參(亞甲基膦酸) (NOTP)、羥乙基二膦酸鹽、氮基參(亞甲基)膦酸、2-膦醯基-丁烷-1,2,3,4-四甲酸、羧基乙基膦酸、胺基乙基膦酸、草甘膦、乙二胺四(亞甲基膦酸)苯基膦酸、其鹽及其衍生物)及/或羧酸(例如,草酸、琥珀酸、馬來酸、蘋果酸、丙二酸、己二酸、酞酸、檸檬酸、檸檬酸鈉、檸檬酸鉀、檸檬酸銨、丙三羧酸、三羥甲基丙酸、吡啶甲酸、吡啶二甲酸、水楊酸、磺基水楊酸、磺基酞酸、磺基琥珀酸、無水甜菜鹼、葡糖酸、酒石酸、葡糖醛酸、2-羧基吡啶)及/或磺酸,諸如4,5-二羥基-1,3-苯二磺酸二鈉鹽。於某些實施例中,該錯合劑包括氮基(參亞甲基膦酸)及亞胺基二乙酸。於某些實施例中,該至少一種錯合劑包括選自單乙醇胺、三乙醇胺、硫酸、檸檬酸及其組合之物質。於一個實施例中,錯合劑於組合物中之量係於基於該移除組合物之總重量計約0.01重量%至約10重量%之範圍內。
於一個實施例中,該錯合劑係選自1-羥基亞乙基-1,1-二膦酸、1,5,9-三氮雜環十二烷-N,N',N''-參(亞甲基膦酸)、1,4,7,10-四氮雜環十二烷-N,N',N'',N'''-肆(亞甲基膦酸)、氮基參(亞甲基)三膦酸、二伸乙基三胺五(亞甲基膦酸)、琥珀酸、檸檬酸、檸檬酸銨、酒石酸、亞胺基二乙酸、胺基三(亞甲基膦酸)、雙(六亞甲基)三胺膦酸、1,4,7-三氮雜環壬烷-N,N',N''-參(亞甲基膦酸)、其鹽及其衍生物。於一個實施例中,該錯合劑為1-羥基亞乙基-1,1-二膦酸或其鹽。
於一個實施例中,該胺基(C
8-C
12烷基)醇係選自3-胺基-4-辛醇、DL-2-胺基-1-己醇、2-(丁胺基)乙醇、1-胺基環己醇及8-胺基-1-辛醇。於一個實施例中,該胺基(C
6-C
10烷基)醇包括3-胺基-4-辛醇。
如上所指定,本發明之組合物不含選自含胍官能基化合物、含吡唑酮官能基化合物或羥基喹啉化合物之腐蝕抑制劑。於另一實施例中,本發明之組合物亦不含選自草酸、琥珀酸、L-酒石酸及其組合之腐蝕抑制劑。於另一實施例中,該等組合物不含任何腐蝕抑制劑。
於另一態樣中,本發明提供組合物,其包含:
a.水;
b.氫氧化膽鹼;
c. 1-羥基亞乙基-1,1-二膦酸;或
d.單乙醇胺;及
e.胺基(C
6-C
10烷基)醇;
其中該組合物不含選自含胍官能基化合物、含吡唑酮官能基化合物或羥基喹啉化合物之腐蝕抑制劑。
於一個實施例中,該胺基(C
8-C
12烷基)醇係選自3-胺基-4-辛醇、DL-2-胺基-1-己醇、2-(丁胺基)乙醇、1-胺基環己醇及8-胺基-1-辛醇。於另一實施例中,該胺基(C
8-C
12烷基)醇包括3-胺基-4-辛醇。於另一實施例中,該組合物基本上由以上組分a.至e.組成。
於本發明之態樣之另外實施例中,該等組合物進一步包含水可分散性或水溶性聚合物。當存在時,此等聚合物包括(但不限於)甲基丙烯酸均聚物及與(例如)丙烯醯胺基甲基丙磺酸及馬來酸之共聚物;馬來酸/乙烯基醚共聚物;聚(乙烯基吡咯啶酮)/乙酸乙烯酯;均聚物,諸如磷酸化之聚乙二醇低聚物、聚(丙烯酸) (PAA)、聚(丙烯醯胺)、聚(乙酸乙烯酯)、聚(乙二醇) (PEG)、聚丙二醇(PPG)、聚(苯乙烯磺酸)、聚(乙烯基磺酸)、聚(乙烯基膦酸)、聚(乙烯基膦酸)、聚(乙烯亞胺)、聚(丙烯亞胺)、聚烯丙胺、聚環氧乙烷(PEO)、聚乙烯基吡咯啶酮(PVP)、PPG-PEG-PPG嵌段共聚物、PEG-PPG-PEG嵌段共聚物、聚(乙烯醇)、聚(羥乙基)丙烯酸酯、聚(羥乙基)甲基丙烯酸酯、羥乙基纖維素、甲基羥乙基纖維素、羥丙基纖維素、甲基羥丙基纖維素、黃原膠、藻酸鉀、果膠、羧甲基纖維素、葡糖胺、聚(二烯丙基二甲基銨)氯化物、PEG化(即,聚乙二醇化)甲基丙烯酸酯/丙烯酸酯共聚物、聚MADQuat (聚(2-甲基丙烯醯氧基乙基三甲基氯化銨) CAS號26161-33-1)及其共聚物、二甲胺基甲基丙烯酸酯聚合物及其共聚物、三甲基銨甲基丙烯酸甲酯聚合物及其共聚物、及其組合。以上共聚物可為無規或嵌段共聚物。當存在時,聚合物於組合物中之量係於基於該組合物之總重量計約0.0001重量%至約5重量%之範圍內。
於另一實施例中,該組合物進一步包含表面活性劑。如本文中所用,術語「表面活性劑」係指降低兩種液體之間或液體與固體之間之表面張力(或介面張力)之有機化合物,通常含有疏水性基團(例如,烴(例如,烷基) 「尾」)及親水性基團之有機兩親性化合物。當存在時,用於本文中所述組合物中之表面活性劑包括(但不限於)兩性鹽、陽離子表面活性劑、陰離子表面活性劑、兩性離子表面活性劑、非離子表面活性劑及其組合,包括(但不限於)癸基膦酸、十二烷基膦酸(DDPA)、十四烷基膦酸、十六烷基膦酸、雙(2-乙基己基)膦酸鹽、十八烷基膦酸、全氟庚酸、全氟癸酸、三氟甲磺酸、膦醯基乙酸、十二烷基苯磺酸(DDBSA)、苯磺酸或其鹽(視情況經一或多個C
8-C
18直鏈或分支鏈烷基取代)、十二烯基琥珀酸、二十八烷基膦酸氫鹽、十八烷基膦酸二氫鹽、十二烷基胺、十二烯基琥珀酸單二乙醇醯胺、月桂酸、棕櫚酸、油酸、檜酸、12-羥基硬脂酸、十八烷基膦酸(ODPA)、十二烷基膦酸鹽。涵蓋之非離子表面活性劑包括(但不限於)聚氧乙烯月桂基醚、十二烯基琥珀酸單二乙醇醯胺、乙二胺肆(乙氧基化合物-嵌段-丙氧基化合物)四醇、聚乙二醇、聚丙二醇、聚乙二醇或聚丙二醇醚、基於環氧乙烷及環氧丙烷之嵌段共聚物、聚氧丙烯蔗糖醚、第三辛基苯氧基聚乙氧基乙醇、10-乙氧基-9,9-二甲基癸-1-胺、聚氧乙烯(9)壬基苯基醚、分支鏈聚氧乙烯(40)壬基苯基醚、分支鏈二壬基苯基聚氧乙烯、壬基酚烷氧基化物、聚氧乙烯山梨糖醇六油酸酯、聚氧乙烯山梨糖醇四油酸酯、聚乙二醇脫水山梨糖醇單油酸酯、脫水山梨糖醇單油酸酯、醇烷氧基化物、烷基-聚葡糖苷、全氟丁酸乙酯、1,1,3,3,5,5-六甲基-1,5-雙[2-(5-降冰片烯-2-基)乙基]三矽氧烷、單體十八烷基矽烷衍生物、經矽氧烷改性之聚矽氮烷、聚矽氧-聚醚共聚物及乙氧基化含氟表面活性劑。涵蓋之陽離子表面活性劑包括(但不限於)鯨蠟基三甲基溴化銨(CTAB)、十七烷基氟辛磺酸、四乙基銨、硬脂醯基三甲基氯化銨、4-(4-二乙胺基苯基偶氮基)-1-(4-硝基苄基)吡啶溴化物、鯨蠟基吡啶氯化物單水合物、苯紮氯銨、苄索氯銨(benzethonium chloride)、苄基二甲基十二烷基氯化銨、苄基二甲基十六烷基氯化銨、十六烷基三甲基溴化銨、二甲基二-(十八烷基)氯化銨、十二烷基三甲基氯化銨、十六烷基三甲基對甲苯磺酸銨、二-(十二烷基)二甲基溴化銨、二(氫化牛脂)二甲基氯化銨、四庚基溴化銨、肆(癸基)溴化銨及奧芬溴銨(oxyphenonium bromide)、鹽酸胍(C(NH2) 3Cl)或三氟甲磺酸鹽諸如四丁基三氟甲磺酸銨、二甲基二-(十八烷基)氯化銨、二甲基二-(十六烷基)溴化銨、二(氫化牛脂)二甲基氯化銨及聚氧乙烯(16)牛脂乙基乙硫酸銨。涵蓋之陰離子表面活性劑包括(但不限於)聚(丙烯酸鈉鹽)、聚丙烯酸銨、聚氧乙烯月桂基醚鈉、二己基磺基琥珀酸鈉、十二烷基硫酸鈉、二辛基磺基琥珀酸鹽、2-磺基琥珀酸鹽、2,3-二巰基-1-丙磺酸鹽、二環己基磺基琥珀酸鈉鹽、7-乙基-2-甲基-4-十一烷基硫酸鈉、磷酸鹽含氟表面活性劑、含氟表面活性劑及聚丙烯酸酯。兩性離子表面活性劑包括(但不限於)炔二醇或經改性之炔二醇、環氧乙烷烷基胺、N,N-二甲基十二烷基胺N-氧化物、椰油丙酸鈉、3-(N,N-二甲基豆蔻基胺基)丙磺酸酯及(3-(4-庚基)苯基-3-羥丙基)二甲胺基丙磺酸酯。
於另一實施例中,該組合物進一步包含水可混溶溶劑及/或佐劑。
於一個實施例中,該水可混溶溶劑係選自二醇及二醇醚、甲醇、乙醇、異丙醇、丁醇及選自C
2-C
4二醇及C
2-C
4三醇、四氫呋喃甲醇之高碳數醇(諸如3-氯-1,2-丙二醇、3-氯-1-丙硫醇、1-氯-2-丙醇、2-氯-1-丙醇、3-氯-1-丙醇、3-溴-1,2-丙二醇、1-溴-2-丙醇、3-溴-1-丙醇、3-碘-1-丙醇、4-氯-1-丁醇、2-氯乙醇)、二氯甲烷、氯仿、乙酸、丙酸、三氟乙酸、四氫呋喃、N-甲基吡咯啶酮、環己基吡咯啶酮、N-辛基吡咯啶酮、N-苯基吡咯啶酮、甲基二乙醇胺、甲酸甲酯、二甲基甲醯胺、二甲亞碸、四亞甲基碸、乙醚、苯氧基-2-丙醇、丙醯苯、乳酸乙酯、乙酸乙酯、苯甲酸乙酯、乙腈、丙酮、乙二醇、丙二醇、1,3-丙二醇、二噁烷、丁醯內酯、碳酸伸丁酯、碳酸乙二酯、碳酸丙二酯、二丙二醇、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、三乙二醇單丁醚、乙二醇單己醚、二乙二醇單己醚、乙二醇苯基醚、丙二醇甲醚、二丙二醇甲醚、三丙二醇甲醚、二丙二醇二甲醚、二丙二醇乙醚、丙二醇正丙醚、二丙二醇正丙醚、三丙二醇正丙醚、丙二醇正丁醚、二丙二醇正丁醚、三丙二醇正丁醚、丙二醇苯醚、乙二醇單苯醚、二乙二醇單苯醚、六乙二醇單苯醚、二丙二醇甲醚乙酸酯、四乙二醇二甲醚、二元酯、碳酸甘油酯、N-甲醯基嗎啉、膦酸三乙酯、單醣及二醣(包括但不限於木糖醇、果糖、蔗糖、葡萄糖、肌糖、半乳糖、麥芽糖)及其組合。
另外示例性佐劑及/或溶劑包括甘油、山梨醇、二醇醚、尿素及雙氰胺。
於一個實施例中,該等佐劑係選自功能為氫鍵結添加劑之化合物,該等添加劑用於減少二氧化矽粒子黏至於CMP後微電子裝置之清潔中所利用之刷子。參見,例如,美國專利公開案第2019/0168265號,其係以引用的方式併入本文中。示例性化合物包括非離子、陰離子、陽離子及兩性離子小分子及可在中性pH下表現為聚電解質之聚合物。陰離子聚合物或陰離子聚電解質可為天然聚合物、經改性之天然聚合物或合成聚合物。可包含於組合物中之示例性天然及經改性之天然陰離子聚合物包括(但不限於)藻酸(或鹽)、羧甲基纖維素、硫酸葡聚糖、聚(半乳糖醛酸)及其鹽。示例性合成陰離子聚電解質包括(但不限於):(甲基)丙烯酸(或鹽)、聚(丙烯酸)、馬來酸(或酸酐)、苯乙烯磺酸(或鹽)、乙烯基磺酸(或鹽)、烯丙基磺酸(或鹽)、丙烯醯胺基丙基磺酸(或鹽)及類似者之均聚物或共聚物,其中羧酸及磺酸之鹽較佳地經銨或烷基銨陽離子中和。於一個實施例中,聚電解質陰離子聚合物之陽離子為銨陽離子(NH
4 +)、膽鹼鎓
+N(CH
3)
3(CH
2CH
2OH)及
+N(CH
3)
4。因此,組合之合成及天然聚電解質陰離子聚合物之實例為(甲基)丙烯酸、馬來酸(或酸酐)、苯乙烯磺酸、乙烯基磺酸、烯丙基磺酸、乙烯基膦酸、丙烯醯胺基丙基磺酸、藻酸、羧甲基纖維素、硫酸葡聚糖、聚(半乳糖醛酸)及其鹽之均聚物或共聚物。
陽離子聚合物及陽離子聚電解質可為天然聚合物、經改性之天然聚合物或合成聚合物。示例性天然及經改性之天然陽離子聚合物包括(但不限於):殼聚糖、陽離子澱粉、聚離胺酸及其鹽。示例性陽離子合成聚電解質包括(但不限於):二烯丙基二甲基氯化銨(DADMAC)、二烯丙基二甲基溴化銨、二烯丙基二甲基硫酸銨、二烯丙基二甲基膦酸銨、二甲基烯丙基二甲基氯化銨、二乙基烯丙基二甲基氯化銨、二烯丙基二(β-羥乙基)氯化銨、二烯丙基二(β-乙氧基乙基)氯化銨、(甲基)丙烯酸二甲胺基乙酯酸加成鹽及四級鹽、(甲基)丙烯酸二乙胺基乙酯酸加成鹽及四級鹽、(甲基)丙烯酸7-胺基-3,7-二甲基辛酯酸加成鹽及四級鹽、N,N'-二甲胺基丙基丙烯醯胺酸加成鹽及四級鹽(其中該等四級鹽包括烷基及苄基季胺化之鹽)、烯丙胺、二烯丙胺、乙烯胺(藉由乙烯基烷基醯胺聚合物之水解獲得)、乙烯基吡啶、殼聚糖、陽離子澱粉、聚離胺酸及其鹽之均聚物或共聚物。
其他實例包括2-吡咯啶酮、1-(2-羥乙基)-2-吡咯啶酮(HEP)、甘油、1,4-丁二醇、四亞甲基碸(環丁碸)、二甲基碸、乙二醇、丙二醇、二丙二醇、四乙二醇二甲醚及二乙二醇二甲醚。
或者,或此外,該等氫鍵結添加劑包括羥丙基纖維素、羥乙基纖維素、羥乙基甲基纖維素、羥丙基甲基纖維素、羧甲基纖維素、羧甲基纖維素鈉、聚乙烯吡咯啶酮(PVP)、使用N-乙烯基吡咯啶酮單體製得之任何聚合物、聚丙烯酸酯及聚丙烯酸酯之類似物、聚胺基酸(例如,聚丙胺酸、聚白胺酸、聚甘胺酸)、聚醯胺基羥基胺基甲酸酯、聚內酯、聚丙烯醯胺、黃原膠、殼聚糖、聚環氧乙烷、聚乙烯醇(PVA)、聚乙酸乙烯酯、聚丙烯酸、聚乙烯亞胺、糖醇(諸如山梨醇、蔗糖、果糖、乳糖、半乳糖、麥芽糖、赤蘚糖醇、麥芽糖醇、蘇糖醇、阿拉伯糖醇、核糖醇、甘露醇、半乳糖醇、肌醇及木糖醇)、脫水山梨糖醇之酯、二級醇乙氧基化物(諸如TERGITOL™表面活性劑)、多官能基醇(包括新戊四醇、二新戊四醇、三羥甲基丙烷、二甲基丙酸及木糖酸)、核鹼基(諸如尿嘧啶、胞嘧啶、鳥嘌呤、胸腺嘌呤)及其組合。
氫鍵結添加劑之還有其他實例包括乳酸、馬來酸、尿素、乙醇酸、山梨醇、硼砂(即,硼酸鈉)、脯胺酸、甜菜鹼、甘胺酸、組胺酸、TRIS (參(羥甲基)胺基甲烷)、二甲亞碸、環丁碸、甘油、SDS (十二烷基硫酸鈉)、十二烷基膦酸或其組合。
於另一實施例中,該組合物進一步包含殺生物劑。示例性殺生物劑包括5-氯-2-甲基-4-異噻唑啉-3-酮、2-甲基-4-異噻唑啉-3-酮、苯并異噻唑酮、1,2-苯并異噻唑-3[2H]-酮、甲基異噻唑啉酮、甲基氯異噻唑啉酮及其組合。
於其他實施例中,本發明之組合物包含:
A.針對具有鎢表面之微電子裝置:
3-胺基-4-辛醇,
山梨醇,
甘油,
聚(苯乙烯磺酸),
聚丙烯酸,
乙醇胺,
依替膦酸(etidronic acid),
檸檬酸,
羥乙基纖維素,
乙醇胺,
氫氧化膽鹼,
三乙醇胺,
苯并異噻唑啉酮,及
磷酸;
B.針對具有鈷表面及疏水性介電質表面之微電子裝置:
3-胺基-4-辛醇,
聚(乙烯基吡咯啶酮),
乙醇胺,
氫氧化膽鹼,
KOH,
依替膦酸,
三乙二醇單丁醚,及
Brij 23 (乙氧基化C
12醇);及
C.針對具有銅表面之微電子裝置:
3-胺基-4-辛醇,
聚(乙烯基吡咯啶酮),
乙醇胺,
氫氧化膽鹼,
KOH,
依替膦酸,
三乙二醇單丁醚,
半胱胺酸,
嗎啉,
琥珀酸,
草酸,
酒石酸,
雙氰胺,
丙二醇單丁醚,及
二乙二醇單丁醚。
如本文中所用,術語「殘留物」(其包含「污染物」)係指為於用於製造微電子裝置之加工步驟,例如包括電漿蝕刻、電漿灰化(以將光阻劑自經蝕刻晶圓移除)、化學-機械加工、濕法蝕刻等之加工步驟後仍存在於微電子裝置基板表面處之化學物或微粒材料的任何材料。該殘留物可為任何非水性化學材料,其為用於加工步驟中之加工組合物之一部分,諸如化學蝕刻劑、光阻劑、CMP漿液等。該殘留物或者可為在加工步驟期間自加工組合物之材料衍生之物質。此等類型之殘留物之實例包括於加工後仍在基板表面處之非水性微粒或非微粒化學或磨料材料(例如,磨料粒子、表面活性劑、氧化劑、腐蝕抑制劑、觸媒)。該殘留物可最初存在於諸如CMP漿液或蝕刻組合物之材料中,諸如存在於CMP研磨漿液中之固體磨料粒子或化學品材料。或者,殘留物可為在加工期間產生之副產物或反應產物(呈微粒(例如,聚集物、沉澱)或非微粒形式),例如,於加工組合物(諸如CMP漿液或濕法蝕刻組合物)中存在之化學品,或在電漿蝕刻或電漿灰化製程期間存在、使用或產生之化學品之副產物或反應產物。
術語「CMP後殘留物」係指在CMP加工步驟結束時存在之殘留物,例如,於CMP漿液中存在或自CMP漿液衍生之粒子或化學品材料;特定實例包括磨料粒子(例如,含二氧化矽或二氧化矽基磨料粒子、金屬氧化物(例如,氧化鋁)粒子、二氧化鈰或二氧化鈰基粒子及類似者);最初存在於漿液中之化學品,諸如氧化劑、觸媒、表面活性劑、抑制劑、錯合劑等;自正在加工之基板表面移除之金屬材料衍生之金屬(例如,鐵)、金屬氧化物或金屬錯合物;或使用漿液之化學品與漿液之另一化學品或與源自基板之化學品材料(諸如金屬離子)產生之反應產物或錯合物;墊粒子或為CMP製程之產物之任何其他材料。
「蝕刻後殘留物」係指於氣相電漿蝕刻製程(例如,線後端(「BEOL」)雙鑲嵌加工或濕法蝕刻製程)後保留之材料。蝕刻後殘留物本質上可係有機、有機金屬、有機矽或無機,例如,含矽材料、碳基有機材料及蝕刻氣體殘留物(諸如氧及氟)。
「灰化後殘留物」係指於氧化性或還原性電漿灰化以移除硬化光阻劑及/或底部抗反射塗層(BARC)材料後保留之材料。灰化後殘留物本質上可係有機、有機金屬、有機矽或無機。
如本文中所用,「低k介電材料」為於多層微電子裝置中用作介電材料之材料,其中該材料具有小於約3.5之介電常數。示例性低k介電材料包括低極性材料,諸如含矽有機聚合物、含矽雜化有機-無機材料、有機矽酸鹽玻璃(OSG)、原矽酸四乙酯(TEOS)、氟化矽酸鹽玻璃(FSG)及摻雜碳之氧化物(CDO)玻璃。低k介電材料可具有來自可用密度範圍及來自可用孔隙率範圍之密度及孔隙率。
如以上所指定,本發明係關於可用於清潔方法中之組合物(「清潔組合物」或「清潔溶液」),該方法自其上具有殘留物之微電子裝置基板移除殘留物。所述組合物為鹼性組合物,其含有水性載劑(即,水)連同非水性成分之組合,該等非水性成分包括:錯合劑及胺基(C
6-C
12烷基)醇。於某些實施例中,在用於清潔製程之前,該等組合物為包含水及所溶解之非水性成分,由其組成,或基本上由其組成之均勻溶液,不存在任何固體或懸浮材料,諸如固體磨料粒子、聚結物、凝結物等。
如所述組合物可用於清潔微電子裝置及其前驅體,尤其包括微電子裝置基板,意指半導體晶圓在表面上包括一或多個微電子裝置或處在製造成最終完成且功能性微電子裝置之製程中的其前驅體。如本文中所用,微電子裝置為包含電路及其上形成之極小(例如,微米尺度或更小)尺寸之相關結構之裝置。示例性微電子裝置包括平板顯示器、積體電路、記憶裝置、太陽能面板、光伏打及微電機系統(MEMS)。微電子裝置基板為諸如晶圓(例如,半導體晶圓)之結構,其包含一或多個微電子裝置或處於正在製備以形成最終微電子裝置之狀態之其前驅體。
本文中所述之組合物及方法可用於在加工之任何階段清潔各種形式之微電子裝置中之任一者。可以特定效用及效益進行清潔之微電子裝置基板(或本文中簡稱為「基板」)包括在基板表面處包含暴露之鈷、鎢、鉬或介電質或所有三者之基板。
根據本發明,該等組合物可用於清潔此等一般類型及特定類型之微電子裝置基板以移除殘留物,諸如(但不限於) CMP後殘留物、灰化後殘留物、蝕刻後殘留物、或於加工微電子裝置基板之步驟後存在於基板表面處之其他殘留物。該等清潔組合物提供有用或有利清潔性質,意指該等清潔組合物能併與已知設備(例如,CMP後清潔設備)使用以實質上減少微電子裝置基板表面上之殘留物、污染物或二者之量,對此等鈷、鎢及介電質表面具有改善之不利效應程度。存在於基板表面處之高百分比之殘留物可藉由使用本文中所述之清潔組合物及方法自表面成功移除,例如,可移除至少70、80、85、90、95或99%之殘留物(亦稱作「清潔效率」)。
用於量測微電子裝置基板表面處之殘留物之方法及設備係熟知。清潔功效可基於清潔後存在於微電子裝置表面上之殘留物粒子之量(例如,數目)與在清潔之前存在之殘留物粒子之量(例如,數目)相比減少來評定。例如,可使用原子力顯微鏡進行清潔前及清潔後分析。表面上之殘留物粒子可登記為像素之範圍。可應用直方圖(例如,Sigma Scan Pro)以過濾某個強度(例如,231至235)之像素,及將殘留物粒子之數目計數。殘留物粒子移除之量(即,清潔效率)可使用以下比率進行計算:
(表面上之清潔前殘留物粒子之數目-表面上之清潔後殘留物粒子之數目)
/(表面上之清潔前殘留物粒子之數目)。
或者,清潔功效可考慮為在清潔之前如與在清潔後相比由殘留微粒物質覆蓋之基板表面之總量之百分比。例如,可將原子力顯微鏡程式化以進行z-平面掃描以識別高於某個高度臨限值之受關注地形區域,及然後計算由受關注區域覆蓋之總表面之面積。於清潔後,測定為受關注區域之面積之減少之量指示更有效清潔組合物及清潔製程。
除了良好清潔功效外,如所述之清潔製程及清潔組合物亦產生經清潔之基板表面,該基板表面受暴露之金屬表面(諸如暴露之金屬鎢、鉬、暴露之金屬鈷或暴露之介電質)之有利低量腐蝕影響。可藉由此製程清潔之示例性基板為在表面處具有金屬鎢或金屬鈷,例如,作為金屬互連(例如,鎢或鈷互連)或位於金屬互連與介電質或介電材料之間之障壁層材料(例如,鈷)之基板。以特別有用或有利結果進行清潔之微電子裝置基板之某些實例包括在表面處含有暴露之結構(其包含金屬鎢(例如,鎢或其合金)、金屬鈷(例如,鈷或其合金)及介電材料)之彼等。清潔組合物之腐蝕抑制可於量測金屬蝕刻速率(諸如靜態蝕刻速率)中反映,該量測可藉由已知方法使用已知設備進行。
可製備本發明之組合物及然後以濃縮物之形式銷售,該濃縮物含有相對低量之水,及因此,相對濃縮量之非水性成分。該濃縮物在市面上經製備以銷售及運輸,同時含有濃縮量之非水性成分及相對減少量之水,及在使用點時由濃縮物之購買者最終稀釋。濃縮物中之不同非水性成分之量為在稀釋濃縮物後將導致存在於使用組合物中之彼等非水性成分之所需量的量。
如所述之組合物包含水作為液體載劑,即,非水性成分之溶質。該水可為去離子(DIW)水。水可自任何來源存在於組合物中,諸如藉由含於與其他成分組合以產生濃縮物形式之組合物之成分中;或作為以純形式與濃縮物之其他成分組合之水;或作為(例如)在使用點時由使用者添加至濃縮物之水,作為出於稀釋濃縮物以形成使用組合物之目的之稀釋水。
組合物中之水之量可為濃縮物之所需量,或使用組合物之所需量,其一般為相對於濃縮物中之水之量之更高總量。濃縮組合物中之水之示例性量(不被視為限制性)可為基於濃縮組合物之總重量計約30、40或50至約85或90重量%,例如,約60、65或70至約80重量%水。在稀釋後,此等量將以稀釋倍率減少。使用組合物中之水之示例性量可為基於使用組合物之總重量計約75至約95重量%,例如,約82或85至約90或93重量%水。
本發明之組合物含有胺基(C
6-C
12烷基)醇作為主要清潔化合物。作為次要清潔化合物,該等組合物可視情況進一步含有C
2-C
4烷醇胺(諸如單乙醇胺)作為次要清潔化合物。
於另一實施例中,該組合物進一步包含另外清潔化合物。此等另外清潔化合物之一些特定實例包括:
a.嗎啉、L-半胱胺酸、雙氰胺、羥基乙基纖維素、聚乙烯基吡咯啶酮、聚胺、及其組合;及
b.藻酸及其鹽;羧甲基纖維素;硫酸葡聚糖及其鹽;聚(半乳糖醛酸)及其鹽;(甲基)丙烯酸及其鹽、馬來酸、馬來酸酐、苯乙烯磺酸及其鹽、乙烯基磺酸及其鹽、烯丙基磺酸及其鹽、丙烯醯胺基丙基磺酸及其鹽之均聚物;(甲基)丙烯酸及其鹽、馬來酸、馬來酸酐、苯乙烯磺酸及其鹽、乙烯基磺酸及其鹽、烯丙基磺酸及其鹽、丙烯醯胺基丙基磺酸及其鹽之共聚物;殼聚糖;陽離子澱粉;聚離胺酸及其鹽;二烯丙基二甲基氯化銨(DADMAC)、二烯丙基二甲基溴化銨、二烯丙基二甲基硫酸銨、二烯丙基二甲基膦酸銨、二甲基烯丙基二甲基氯化銨、二乙基烯丙基二甲基氯化銨、二烯丙基二(β-羥乙基)氯化銨、二烯丙基二(β-乙氧基乙基)氯化銨、(甲基)丙烯酸二甲胺基乙酯酸加成鹽及四級鹽、(甲基)丙烯酸二乙胺基乙酯酸加成鹽及四級鹽、(甲基)丙烯酸7-胺基-3,7-二甲基辛酯酸加成鹽及四級鹽、N,N'-二甲胺基丙基丙烯醯胺酸加成鹽及四級鹽、烯丙胺、二烯丙胺、乙烯胺、乙烯基吡啶之均聚物;及二烯丙基二甲基氯化銨、二烯丙基二甲基溴化銨、二烯丙基二甲基硫酸銨、二烯丙基二甲基膦酸銨、二甲基烯丙基二甲基氯化銨、二乙基烯丙基二甲基氯化銨、二烯丙基二(β-羥乙基)氯化銨、二烯丙基二(β-乙氧基乙基)氯化銨、(甲基)丙烯酸二甲胺基乙酯酸加成鹽及四級鹽、(甲基)丙烯酸二乙胺基乙酯酸加成鹽及四級鹽、(甲基)丙烯酸7-胺基-3,7-二甲基辛酯酸加成鹽及四級鹽、N,N'-二甲胺基丙基丙烯醯胺酸加成鹽及四級鹽、烯丙胺、二烯丙胺、乙烯胺、乙烯基吡啶之共聚物;椰油基二甲基羧甲基甜菜鹼;月桂基二甲基羧甲基甜菜鹼;月桂基二甲基-α-羧乙基甜菜鹼;鯨蠟基二甲基羧甲基甜菜鹼;月桂基-雙(2-羥乙基)羧甲基甜菜鹼;硬脂醯基-雙(2-羥丙基)羧甲基甜菜鹼;油烯基二甲基-γ-羧丙基甜菜鹼;月桂基-雙(2-羥丙基)α-羧乙基甜菜鹼;椰油基二甲基磺丙基甜菜鹼;硬脂醯基二甲基磺丙基甜菜鹼;月桂基-雙(2-羥乙基)磺丙基甜菜鹼;十二烷基硫酸鈉;二辛基磺基琥珀酸鈉鹽;月桂基醚硫酸鈉;分支鏈聚乙二醇-壬基苯基醚硫酸銨鹽;2-十二烷基-3-(2-磺酸根基苯氧基)二鈉;PEG25-PABA;聚乙二醇單C
10-
16烷基醚硫酸鈉鹽;(2-N-丁氧乙氧基)乙酸;十六烷基苯磺酸;鯨蠟基三甲基氫氧化銨;十二烷基三甲基氫氧化銨;十二烷基三甲基氯化銨;鯨蠟基三甲基氯化銨;N-烷基-N-苄基-N,N-二甲基氯化銨;十二烷胺;聚氧乙烯月桂基醚;十二烯基琥珀酸單二乙醇醯胺;乙二胺肆(乙氧基化物-嵌段-丙氧基化物);2-吡咯啶酮;1-(2-羥乙基)-2-吡咯啶酮(HEP)。
本發明之組合物可藉由簡單添加各自成分及混合至均勻條件(諸如溶液)容易製備。此外,組合物可容易調配成單包裝調配物或在使用點時或在使用點之前混合之多部分調配物,例如,多部分調配物之個別部分可由使用者在加工工具(清潔裝置)處或於加工工具上游之儲存槽中混合。
因此,本發明之另一態樣係關於套組,其於一或多個容器中包含如本文中所闡述之組合物之一或多種組分。該套組可於一或多個容器中包含(i) pH調節劑;(ii)錯合劑;(iii)胺基(C
6-C
10烷基)醇,用於在晶圓廠或使用點時與另外溶劑(例如,水)組合。該套組亦可包含本文中所詳述之其他視情況可選的成分。套組之容器必須適用於儲存及船運組合物並可為(例如) NOWPak®容器(Entegris, Inc., Billerica, Mass., USA)。
另外,如本文中所述之組合物可以濃縮物之形式在市面上提供用於銷售,可在使用點時將該濃縮物利用適宜量之水稀釋。以濃縮物形式,該組合物(濃縮物)包含如本文中所闡述之非水性成分,其將以使得當將濃縮物用所需量之水(例如,DI水)稀釋時,清潔組合物之各組分將以用於清潔步驟(諸如CMP後清潔步驟)所需之量存在於經稀釋之使用組合物中的量存在於濃縮物中。添加至濃縮物中以形成使用組合物之水之量可為一或多體積之水/體積之濃縮物,例如,2體積之水(例如,3、4、5或10體積之水)/體積之濃縮物。當將濃縮物用此量之水稀釋時,濃縮物之固體組分各者將以某種濃度存在於使用組合物中,該濃度基於經添加以稀釋濃縮物之水之體積數減少。
如所述之清潔組合物可用於微電子裝置加工應用中,該等應用包括藉由諸如蝕刻後殘留物移除、灰化後殘留物移除表面製備、CMP後殘留物移除及類似者之方法清潔基板表面之製程。可藉由此製程清潔之示例性基板包括包含金屬鎢、金屬鈷、低k介電材料或所有三者之基板。
清潔組合物及清潔方法對自表面移除相對於在清潔步驟之前最初存在於表面上之量的實質量之殘留物係有效。同時,該組合物及方法係有效而不對可存在於表面處之介電材料造成不當損害,且不對亦存在於所選基板表面處之諸如金屬鉬、鎢、銅或鈷之材料造成不當腐蝕。於一個實施例中,該清潔組合物可於清潔步驟中有效,以移除至少85%之在藉由清潔步驟移除殘留物之前存在於基板表面上之殘留物,或至少90%之在清潔步驟之前最初存在之殘留物或至少95%之殘留物或至少99%之殘留物。
於清潔步驟(諸如CMP後殘留物清潔步驟)中,清潔組合物可使用各種已知習知市售清潔工具中之任一者,諸如超高頻音波及刷子擦洗,包括(但不限於) Verteq單晶圓超高頻音波Goldfinger、OnTrak系統DDS (雙面洗滌器)、SEZ或其他單晶圓噴霧沖洗、Applied Materials Mirra-Mesa™/Reflexion™/Reflexion LK™、及超高頻音波分批濕式工作臺系統、及Ebara Technologies, Inc.產品,諸如300 mm型號(FREX300S2及FREX300X3SC)及200 mm CMP系統(FREX200M)。
清潔步驟之條件及時序可係如所需,及可取決於基板及殘留物之類型變化。於使用組合物用於自其上具有CMP後殘留物、蝕刻後殘留物、灰化後殘留物或污染物之微電子裝置基板清潔CMP後殘留物、蝕刻後殘留物、灰化後殘留物或污染物中,該清潔組合物可在約20℃至約90℃,或約20℃至約50℃之範圍之溫度下與基板表面接觸約1秒至約20分鐘,例如,約5秒至10分鐘,或約15秒至約5分鐘之時間。此等接觸時間及溫度係說明性,及若對自表面至少部分,較佳地實質上清潔初始量之殘留物有效,則任何其他適宜時間及溫度條件可係可用。
於裝置基板表面之所需程度之清潔後,用於清潔步驟中之清潔組合物可容易自裝置表面移除,如可於給定最終用途應用中所需且有效。例如,移除可藉由使用包含去離子水之沖洗溶液進行。之後,可將裝置如所需進行加工,諸如藉由乾燥(例如,使用氮氣或旋乾循環),接著後續加工經清潔及經乾燥之裝置表面。
於其他更一般或特定方法中,微電子裝置基板可首先經受包含CMP加工、電漿蝕刻、濕法蝕刻、電漿灰化或類似者中之任一者或多者之加工步驟,接著包含將基板表面用本發明之組合物清潔之清潔步驟。在第一加工步驟結束時,殘留物(例如,蝕刻後殘留物、CMP後殘留物、灰化後殘留物等)將存在於基板表面處。使用如所述之清潔組合物之清潔步驟將對自微電子裝置表面清潔實質量之殘留物有效。
因此,於另一態樣中,本發明提供一種自其上具有殘留物之微電子裝置基板移除該等殘留物之方法,其中該基板具有包含選自銅、鈷、鎢或介電質組合物之物質之至少一個表面,該方法包括:
使微電子裝置基板之表面與組合物接觸,該組合物包含:
a.水;
b.錯合劑;及
c.胺基(C
6-C
12烷基)醇;
其中該組合物不含選自含胍官能基化合物、含吡唑酮官能基化合物或羥基喹啉化合物之腐蝕抑制劑,及自該基板至少部分移除該等殘留物。
除非另有明確指定,否則本發明可藉由其較佳實施例之下列實例進一步說明,但是應瞭解,此等實例係僅出於說明目的包含且不意欲限制本發明之範圍。
實例實例1:製備如表1中所提及之溶液1至10及將其用於處理具有銅或鈷表面之微電子裝置基板,以評價相對蝕刻速率。
蝕刻速率為在將表面暴露於某種電解質(諸如清潔組合物)後自金屬表面移除之金屬之量的量度。在30℃溫度及500 rpm 攪拌下的15分鐘清潔製程之前及之後藉由使用X-射線螢光(XRF)量測金屬膜厚度。
表1
*1-羥基亞乙基-1,1-二膦酸
材料 | CAS號 | 1 | 2 | 3 | 4 | 5 | 6 | 7 | 8 | 9 | 10 |
去離子水 | 7732-18-5 | 78.14 | 77.14 | 77.43 | 77.33 | 77.53 | 77.33 | 77.35 | 77.14 | 77.32 | 77.62 |
47%氫氧化膽鹼 | 123-41-1 | 18.00 | 18.00 | 18.00 | 18.00 | 18.00 | 18.00 | 18.00 | 18.00 | 18.00 | 18.00 |
59% HEDP* | 2809-21-4 | 1.36 | 1.36 | 1.36 | 1.36 | 1.36 | 1.36 | 1.36 | 1.36 | 1.36 | 1.36 |
單乙醇胺 | 141-43-5 | 2.50 | 2.50 | 2.50 | 2.50 | 2.50 | 2.50 | 2.50 | 2.50 | 2.50 | 2.50 |
3-胺基-4-辛醇 | 1001354-72-8 | 1.00 | |||||||||
5-胺基-1-戊醇 | 2508-29-4 | 0.71 | |||||||||
DL-2-胺基-1-己醇 | 5665-74-7 | 0.81 | |||||||||
2-胺基-2-甲基-1-丙醇 | 124-68-5 | 0.61 | |||||||||
2-(丁胺基)乙醇 | 111-75-1 | 0.81 | |||||||||
2-胺基環己醇 | 6850-38-0 | 0.79 | |||||||||
8-胺基-1-辛醇 | 19008-71-0 | 1.00 | |||||||||
2-胺基-2-乙基-1,3-丙二醇 | 115-70-8 | 0.82 | |||||||||
3-胺基丙醇 | 156-87-6 | 0.52 | |||||||||
總計(克) | 100 | 100 | 100 | 100 | 100 | 100 | 100 | 100 | 100 | 100 |
此外,如表2中所示,含有如本文中所述之腐蝕抑制劑與特定基底材料Cu及Co之本發明清潔組合物如與對照溶液相比展示更低蝕刻速率。
表2
Cu | Co | |||
平均值 | 標準偏差 | 平均值 | 標準偏差 | |
對照(溶液1) | 5.86 | 0.04 | 2.06 | 0.20 |
對照+ 3-胺基-4-辛醇 | 3.62 | 0.08 | 1.66 | 0.05 |
對照+ 5-胺基-1-戊醇 | 5.80 | 0.06 | 2.09 | 0.25 |
對照+ DL-2-胺基-1-己醇 | 6.03 | 0.10 | 1.99 | 0.24 |
對照+ 2-胺基-2-甲基-1-丙醇 | 6.31 | 0.09 | 2.05 | 0.20 |
對照+ 2-(丁胺基)乙醇 | 5.42 | 0.07 | 1.88 | 0.17 |
對照+ 2-胺基環己醇 | 5.72 | 0.21 | 1.48 | 0.22 |
對照+ 8-胺基-1-辛醇 | 5.20 | 0.02 | 1.86 | 0.12 |
對照+ 2-胺基-2-乙基-1,3-丙二醇 | 5.18 | 0.21 | 1.46 | 0.10 |
對照+ 3-胺基丙醇 | 5.48 | 0.03 | 1.86 | 0.15 |
實例2:製備表3中所示之下列組合物及根據下列程序進行測試:
蝕刻速率程序: 試片製備: 將晶圓切割成具有介於22與24 mm之間之邊尺寸之正方形試片。
將晶圓用清潔壓縮氮氣吹除以移除切割灰塵。噴嘴應距離晶圓表面1”與2”之間。
燒杯加工:
若指定預先量測,則預先量測試片。使用刻參考將試片以可重複方向放置。
設置熱板上之所需加工溫度。於熱板溫度讀出停止閃爍(指示已達到溫度)後,再等待30分鐘,之後加工試片。
準備具有250至350 ml DIW之2個400 ml燒杯以用於沖洗。一個(用於第一沖洗)應位於熱板附近之罩內,及另一個(用於溢流沖洗)應於DIW供應下之水槽中。
使用藍色夾子將試片放置於燒杯中,其中活性側面向化學品之流動。
在所需時間移除所有試片。
將夾子及試片浸入填充有250至350 ml DIW之400 ml特氟龍(Teflon)燒杯中1至3秒。此步驟之目的為移除在溢流沖洗之前黏附至晶圓及夾子之大多數調配物。
將夾子及試片移動至具有連續流之水槽中之燒杯中(溢流沖洗),針對Cu持續2分鐘及針對Co持續10秒。
將DIW自試片吹除。利用壓縮N
2吹除,其中噴嘴距離試片1與2”之間。在夾子對面開始及將N
2物流沿著晶圓向下移動。儘可能多地像床單一樣移動水,避免在晶圓表面上具有小滴乾燥。
後量測試片。
表3
pH = 13.8 | pH = 13.8 | |||
摻合物順序 | 原料 | CAS號 | Co-S1 | Co-S2 |
1 | DIW水 | 7732-18-5 | 77.24 | 76.44 |
3 | HEDP (59%) | 9003-39-8 | 1.36 | 1.36 |
4 | MEA | 141-43-5 | 2.5 | 2.5 |
5 | 3-胺基-4-辛醇 | 1001354-72-8 | 無 | 0.8 |
6 | KOH (45%) | 1310-58-3 | 18.9 | 18.9 |
平均值 | 標準偏差 | |
Co-S1 | 0.493 | 0.087 |
Co-S2 | 0.231 | 0.015 |
實例3:研磨資料:
將表3中所示之樣品A及B用99份水及1份樣品稀釋。將TEOS (二氧化矽)及/或氮化矽晶圓用二氧化矽基市售漿液在Reflexion LK上研磨及然後在積體PVP電刷站上使用Entegris Planarcore
®刷清潔120秒。然後將晶圓藉由KLA-TENCORE SP3在65 nm臨限值處分析及然後藉由SEMVISION SEM劃痕分類及移除凹坑,因為其與清潔製程不相關,及總缺陷為二氧化矽缺陷加上任何有機殘留物缺陷之加總。
本發明已特別參考其某些實施例詳細描述,但是應瞭解,變化及修改可於本發明之精神及範圍內實現。
表3
*無缺陷
樣品 | TEOS缺陷 | Si 3N 4缺陷 | |
A1 (比較例) | 9%檸檬酸,6%山梨醇,0.95%甲酸,0.5%聚(丙烯酸) 0.01%羥乙基纖維素,0.5%磺化聚(丙烯酸) 利用氫氧化膽鹼將pH調整至4.5 | 33 | 282 |
A2 (本發明) | 9%檸檬酸,6%山梨醇,0.95%甲酸,0.5%聚(丙烯酸) 1% 3-胺基-4-辛醇 利用氫氧化膽鹼將pH調整至4.5 | 0 | 0 |
B1 (比較例) | 0.45%乙醇胺,0.26%雙氰胺,0.3%酒石酸,0.03%半胱胺酸,3%丙二醇單丁醚,利用氫氧化膽鹼將pH調整至13.7 | 219 | ND* |
B2 (比較例) | 4.5%乙醇胺,0.1%酒石酸,0.05%半胱胺酸,利用氫氧化膽鹼將pH調整至13.7 | 18 | ND |
B3 (本發明) | 0.65%乙醇胺,0.96%琥珀酸,0.03%半胱胺酸,0.5% 3-胺基-4-辛醇,利用氫氧化膽鹼將pH調整至13.7 | 10 | ND |
Claims (16)
- 一種組合物,其包含: a.水; b.錯合劑;及 c.胺基(C 6-C 12烷基)醇; 其中該組合物不含選自含胍官能基化合物、含吡唑酮官能基化合物或羥基喹啉化合物之腐蝕抑制劑。
- 如請求項1之組合物,其中該胺基(C 6-C 12烷基)醇為胺基(C 8-C 10烷基)醇。
- 如請求項1之組合物,其進一步包含C 2-C 4烷醇胺。
- 如請求項1之組合物,其中該錯合劑係選自 a. 4-(2-羥乙基)嗎啉、1,2-環己二胺-N,N,N',N'-四乙酸、羥乙基乙二胺三乙酸、乙二胺四乙酸、間苯二甲胺、亞胺基二乙酸、三甲胺、異丙醇胺、二異丙醇胺、哌嗪、羥乙基哌嗪、二羥乙基哌嗪、葡糖胺、N-甲基葡糖胺、2-(羥乙基)亞胺基二乙酸、氮基三乙酸、硫脲、1,1,3,3-四甲基脲、脲、尿酸; b.選自以下之胺基酸:丙胺酸、精胺酸、天冬醯胺、天冬胺酸、半胱胺酸、麩胺酸、麩胺醯胺、組胺酸、異白胺酸、白胺酸、離胺酸、甲硫胺酸、苯丙胺酸、脯胺酸、絲胺酸、蘇胺酸、色胺酸、酪胺酸、纈胺酸、牛磺酸、甜菜鹼; c.選自以下之包含膦酸部分之化合物:1-羥基亞乙基-1,1-二膦酸、1,5,9-三氮雜環十二烷-N,N',N''-參(亞甲基膦酸)、1,4,7,10-四氮雜環十二烷-N,N',N'',N'''-肆(亞甲基膦酸)、氮基參(亞甲基)三膦酸、二伸乙基三胺五(亞甲基膦酸)、胺基三(亞甲基膦酸)、雙(六亞甲基)三胺五亞甲基膦酸、1,4,7-三氮雜環壬烷-N,N',N''-參(亞甲基膦酸)、羥乙基二膦酸鹽、氮基參(亞甲基)膦酸;及 d.選自2-膦醯基-丁烷-1,2,3,4-四甲酸、羧基乙基膦酸、胺基乙基膦酸、草甘膦、乙二胺四(亞甲基膦酸)、苯基膦酸之羧酸;選自草酸、琥珀酸、馬來酸、蘋果酸、丙二酸、己二酸、酞酸、檸檬酸、檸檬酸鈉、檸檬酸鉀、檸檬酸銨、丙三羧酸、三羥甲基丙酸、吡啶甲酸、吡啶二甲酸、水楊酸、磺基水楊酸、磺基酞酸、磺基琥珀酸、葡糖酸、酒石酸、葡糖醛酸、2-羧基吡啶之羧酸及/或選自4,5-二羥基-1,3-苯二磺酸二鈉鹽之磺酸。
- 如請求項1之組合物,其中該胺基(C 6-C 10烷基)醇係選自3-胺基-4-辛醇、DL-2-胺基-1-己醇、2-(丁胺基)乙醇、1-胺基環己醇及8-胺基-1-辛醇。
- 如請求項1之組合物,其中該胺基(C 8-C 12烷基)醇包括3-胺基-4-辛醇。
- 如請求項1之組合物,其進一步包含水溶性或水可分散性聚合物。
- 如請求項1之組合物,其進一步包含殺生物劑。
- 如請求項1之組合物,其進一步包含表面活性劑。
- 如請求項1之組合物,其進一步包含水可混溶溶劑及/或佐劑。
- 如請求項1之組合物,其包含: a.水; b.氫氧化膽鹼; c. 1-羥基亞乙基-1,1-二膦酸; d.單乙醇胺;及 e.胺基(C 6-C 10烷基)醇; 其中該組合物不含選自含胍官能基化合物、含吡唑酮官能基化合物或羥基喹啉化合物之腐蝕抑制劑。
- 如請求項1之組合物,其中該組合物為含有小於80重量%水之濃縮物。
- 如請求項1之組合物,其進一步包含選自嗎啉、L-半胱胺酸、雙氰胺、羥基乙基纖維素、聚乙烯吡咯啶酮、聚胺及其組合之化合物。
- 一種自其上具有殘留物之微電子裝置基板移除該等殘留物之方法,其中該基板具有包含選自銅、鈷、鎢、鉬或介電質組合物之物質之至少一個表面,該方法包括: 使該微電子裝置基板之表面與組合物接觸,該組合物包含: a.水; b.錯合劑;及 c.胺基(C 8-C 12烷基)醇; 其中該組合物不含選自含胍官能基化合物、含吡唑酮官能基化合物或羥基喹啉化合物之腐蝕抑制劑,及自該基板至少部分移除該等殘留物。
- 如請求項14之方法,其中該表面包含鈷、銅、鎢及/或鉬中之至少一者。
- 如請求項14之方法,其中該表面為選自以下之介電質:原矽酸四乙酯、含矽有機聚合物、含矽雜化有機-無機材料、有機矽酸鹽玻璃、氟化矽酸鹽玻璃及摻雜碳之氧化物玻璃。
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US20090107520A1 (en) * | 2007-10-29 | 2009-04-30 | Wai Mun Lee | Amidoxime compounds as chelating agents in semiconductor processes |
WO2010048139A2 (en) * | 2008-10-21 | 2010-04-29 | Advanced Technology Materials, Inc. | Copper cleaning and protection formulations |
WO2012067962A1 (en) * | 2010-11-16 | 2012-05-24 | Dow Global Technologies Llc | Hard surface cleaners comprising low voc, low odor alkanolamines |
US11085011B2 (en) * | 2018-08-28 | 2021-08-10 | Entegris, Inc. | Post CMP cleaning compositions for ceria particles |
US11060051B2 (en) * | 2018-10-12 | 2021-07-13 | Fujimi Incorporated | Composition for rinsing or cleaning a surface with ceria particles adhered |
-
2021
- 2021-10-01 EP EP21878266.2A patent/EP4225881A1/en active Pending
- 2021-10-01 US US17/491,750 patent/US20220106541A1/en active Pending
- 2021-10-01 WO PCT/US2021/053096 patent/WO2022076252A1/en unknown
- 2021-10-01 JP JP2023521041A patent/JP2024500596A/ja active Pending
- 2021-10-01 CN CN202180075325.4A patent/CN116438284A/zh active Pending
- 2021-10-01 KR KR1020237014902A patent/KR20230079426A/ko unknown
- 2021-10-04 TW TW110136877A patent/TW202227602A/zh unknown
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Publication number | Publication date |
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JP2024500596A (ja) | 2024-01-10 |
CN116438284A (zh) | 2023-07-14 |
EP4225881A1 (en) | 2023-08-16 |
US20220106541A1 (en) | 2022-04-07 |
KR20230079426A (ko) | 2023-06-07 |
WO2022076252A1 (en) | 2022-04-14 |
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