CN116457447A - 化学机械抛光后(post cmp)清洁组合物 - Google Patents
化学机械抛光后(post cmp)清洁组合物 Download PDFInfo
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- CN116457447A CN116457447A CN202180076458.3A CN202180076458A CN116457447A CN 116457447 A CN116457447 A CN 116457447A CN 202180076458 A CN202180076458 A CN 202180076458A CN 116457447 A CN116457447 A CN 116457447A
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- acid
- ether
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- poly
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- YIOJGTBNHQAVBO-UHFFFAOYSA-N dimethyl-bis(prop-2-enyl)azanium Chemical compound C=CC[N+](C)(C)CC=C YIOJGTBNHQAVBO-UHFFFAOYSA-N 0.000 claims description 8
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- SUVIGLJNEAMWEG-UHFFFAOYSA-N propane-1-thiol Chemical compound CCCS SUVIGLJNEAMWEG-UHFFFAOYSA-N 0.000 claims description 8
- WQGWDDDVZFFDIG-UHFFFAOYSA-N pyrogallol Chemical compound OC1=CC=CC(O)=C1O WQGWDDDVZFFDIG-UHFFFAOYSA-N 0.000 claims description 8
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 claims description 8
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- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 claims description 8
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- RWPGFSMJFRPDDP-UHFFFAOYSA-L potassium metabisulfite Chemical compound [K+].[K+].[O-]S(=O)S([O-])(=O)=O RWPGFSMJFRPDDP-UHFFFAOYSA-L 0.000 claims description 5
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- CDAISMWEOUEBRE-GPIVLXJGSA-N inositol Chemical compound O[C@H]1[C@H](O)[C@@H](O)[C@H](O)[C@H](O)[C@@H]1O CDAISMWEOUEBRE-GPIVLXJGSA-N 0.000 description 1
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- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 238000000206 photolithography Methods 0.000 description 1
- IUGYQRQAERSCNH-UHFFFAOYSA-N pivalic acid Chemical compound CC(C)(C)C(O)=O IUGYQRQAERSCNH-UHFFFAOYSA-N 0.000 description 1
- 238000007747 plating Methods 0.000 description 1
- 229920001308 poly(aminoacid) Polymers 0.000 description 1
- 229920000333 poly(propyleneimine) Polymers 0.000 description 1
- 108010054442 polyalanine Proteins 0.000 description 1
- 108010094020 polyglycine Proteins 0.000 description 1
- 229920000232 polyglycine polymer Polymers 0.000 description 1
- 229920000259 polyoxyethylene lauryl ether Polymers 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- GJAWHXHKYYXBSV-UHFFFAOYSA-N pyridinedicarboxylic acid Natural products OC(=O)C1=CC=CN=C1C(O)=O GJAWHXHKYYXBSV-UHFFFAOYSA-N 0.000 description 1
- HNJBEVLQSNELDL-UHFFFAOYSA-N pyrrolidin-2-one Chemical compound O=C1CCCN1 HNJBEVLQSNELDL-UHFFFAOYSA-N 0.000 description 1
- 229920005604 random copolymer Polymers 0.000 description 1
- 230000009467 reduction Effects 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
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- 150000003384 small molecules Chemical class 0.000 description 1
- 235000019812 sodium carboxymethyl cellulose Nutrition 0.000 description 1
- 229920001027 sodium carboxymethylcellulose Polymers 0.000 description 1
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- FVEFRICMTUKAML-UHFFFAOYSA-M sodium tetradecyl sulfate Chemical compound [Na+].CCCCC(CC)CCC(CC(C)C)OS([O-])(=O)=O FVEFRICMTUKAML-UHFFFAOYSA-M 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 125000004079 stearyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000005720 sucrose Substances 0.000 description 1
- 150000003460 sulfonic acids Chemical class 0.000 description 1
- 239000011885 synergistic combination Substances 0.000 description 1
- 150000005622 tetraalkylammonium hydroxides Chemical class 0.000 description 1
- OKIZCWYLBDKLSU-UHFFFAOYSA-N tetramethylazanium;hydrochloride Chemical compound Cl.C[N+](C)(C)C OKIZCWYLBDKLSU-UHFFFAOYSA-N 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 229940113082 thymine Drugs 0.000 description 1
- IJGSGCGKAAXRSC-UHFFFAOYSA-M tris(2-hydroxyethyl)-methylazanium;hydroxide Chemical compound [OH-].OCC[N+](C)(CCO)CCO IJGSGCGKAAXRSC-UHFFFAOYSA-M 0.000 description 1
- JVFFWGJAAQAIBS-UHFFFAOYSA-K trisodium 2,2-dioctyl-3-sulfonatobutanedioate Chemical compound [Na+].C(CCCCCCC)C(C(C(=O)[O-])S(=O)(=O)[O-])(C(=O)[O-])CCCCCCCC.[Na+].[Na+] JVFFWGJAAQAIBS-UHFFFAOYSA-K 0.000 description 1
- SJEYEFOHSMBQIX-UHFFFAOYSA-N undecane-1-sulfonic acid Chemical compound CCCCCCCCCCCS(O)(=O)=O SJEYEFOHSMBQIX-UHFFFAOYSA-N 0.000 description 1
- 238000011144 upstream manufacturing Methods 0.000 description 1
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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
- C11D7/00—Compositions of detergents based essentially on non-surface-active compounds
- C11D7/22—Organic compounds
- C11D7/26—Organic compounds containing oxygen
- C11D7/267—Heterocyclic 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
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Abstract
本发明大体上提供用于介电表面,如PETEOS、SiO2、热氧化物、氮化硅、硅等的高pH清洁组合物。本发明的组合物提供优越表面润湿、粒子和有机残留物的分散,并且防止经分散的残留物在清洁期间再沉积和再附聚以提供优良清洁和低缺陷率。
Description
技术领域
本发明大体上涉及用于自微电子装置表面移除CMP后残留物的组合物。
背景技术
微电子装置晶圆用于形成集成电路。微电子装置晶圆包含衬底(如硅),衬底中的区域经图案化以沉积具有绝缘、导电或半导电性质的不同材料。
为了获得正确图案化,必须移除用于在衬底上形成层的过量材料。此外,对于制造功能性且可靠电路,在后续加工之前制备平坦或平面微电子晶圆表面是重要的。因此,移除和/或抛光微电子装置晶圆的某些表面是必要的。
化学机械抛光或平坦化("CMP")为其中材料自微电子装置晶圆表面移除,和所述表面通过结合物理工艺(如研磨)与化学工艺(如氧化或螯合)来抛光(例如,平坦化)的工艺。以其最初级形式,CMP涉及将具有活性化学品的磨料浆液施覆到抛光垫,所述抛光垫在移除、平坦化和抛光工艺期间将微电子装置晶圆表面擦亮。使用纯物理或纯化学作用的移除或抛光工艺不如二者的协同组合那样有效以达成快速均匀移除。此外,在集成电路的制造中,CMP浆液也应能优先移除包含金属和其它材料的络合物层的膜使得可产生高度平坦表面用于后续光刻法或图案化、蚀刻和薄膜加工。
在使用浅渠沟隔离(STI)方法于硅衬底中形成隔离区的前端工艺(FEOL)方法中,将垫氧化物膜和垫氮化物膜沉积在半导体衬底上并图案化以暴露衬底的部分,所述部分对应于隔离区。然后,将衬底的经暴露的区域蚀刻以形成渠沟。之后,使衬底经受牺牲氧化工艺以移除由衬底蚀刻造成的损伤,接着在渠沟表面上形成壁氧化物膜。接下来,将沟埋氧化物膜(例如,由高密度等离子体化学气相沉积形成的氧化物膜,称作HDP-氧化物膜)以使得埋于渠沟中的方式沉积在衬底表面。然后,使HDP-氧化物膜的表面经受化学机械抛光直到暴露垫氮化物膜。然后将所得衬底清洁并移除在渠沟蚀刻期间用作蚀刻阻挡的垫氮化物膜,从而完成隔离区的形成。
使用二氧化铈粒子的CMP浆液一般相对于含二氧化硅的浆液达成针对绝缘体的更快抛光速度。此外,最常使用二氧化铈基浆液,因为以最小氧化物腐蚀达成STI图案平坦化的能力。不利地,二氧化铈基浆液难以自STI结构移除,因为二氧化铈粒子相对于氧化硅和氮化硅表面的带相反电荷的ζ电位。若制造具有保留在晶圆上的这些残留物的装置,则所述残留物将导致短路和电阻增加。在使用二氧化铈浆液的CMP加工后,利用FinFET结构,二氧化铈粒子也成问题。
利用含有二氧化硅和其它表面羟化金属氧化物作为磨料粒子的浆液抛光的介电衬底(PETEOS、SiO2、热氧化物、氮化硅、硅等)的CMP后清洁是困难的且导致高的残留物和缺陷率,这是由于磨料粒子与介电表面之间在低和中度pH下经由氢键结和范德华(Van derWaals)力的强烈相互作用和在高pH下粒子附聚和再沉积。理论上,在大于pH IEP(等电点)的pH下,磨料残留物粒子和介电表面二者应高度带负电和因此,静电排斥粒子-衬底应导致更低缺陷率。事实上,大多数CMP浆液有机添加剂将防止并中和这些强烈排斥力,有时促进粒子与晶圆表面的更好粘附,一种会导致高缺陷率的非所需效应。因此,存在对改良的CMP后清洁组合物的需求,所述清洁组合物有效移除残留粒子以及粘附到介电晶圆表面的那些残留物二者。
发明内容
本发明大体上提供用于介电表面(如PETEOS、SiO2、热氧化物、氮化硅、硅等)的高pH清洁组合物。本发明的组合物提供优越表面润湿,粒子和有机残留物的分散,并且防止经分散的残留物在清洁期间的再沉积和再附聚以提供优越清洁和低缺陷率。在一个方面,本发明提供组合物,所述组合物包含:
a.水;
b.具有2到7个碳原子的烷醇胺;
c.二醇醚;
d.pH调节剂;和
e.表面活性疏水性酸。
附图说明
图1为通过粒子计数程序获得的各制剂的粒子面积结果,所述程序后为浸渍试验和SEM测量,比较样品1(比较例)与样品2、3和4。
图2为样品1(比较例)和本发明改良的组合物的表面张力和水接触角(WCA)。
图3说明各种组合物系列的粒子面积结果。
具体实施方式
本发明大体上涉及可用于自其上具有残留物和污染物的微电子装置移除此(等)材料的组合物。所述组合物特别可用于自介电表面(如PETEOS、SiO2、热氧化物、氮化硅、硅等)移除CMP后、蚀刻后、或灰化后残留物。
如本说明书和随附权利要求中所用,除非内容另有明确指定,否则单数形式“一(a/an)”和“所述”包含多个提及物。如本说明书和随附权利要求中所用,除非内容另有明确指定,否则术语“或”一般以其含义包含“和/或”采用。
术语“约”一般是指认为等效于所详述值(例如,具有相同功能或结果)的数字范围。在许多实例中,术语“约”可包含圆整到最近有效数字的数字。
使用端点表示的数值范围包含归入所述范围内的所有数字(例如,1到5包含1、1.5、2、2.75、3、3.80、4和5)。
在第一方面,本发明提供一种组合物,包含:
a.水;
b.具有2到7个碳原子的烷醇胺;
c.二醇醚;
d.pH调节剂;和
e.表面活性疏水性酸。
在一个实施例中,所述烷醇胺选自氨基乙基乙醇胺、N-甲氨基乙醇、氨基乙氧基乙醇、氨基乙氧基乙氧基乙醇、甲氧基丙胺、丁氧基异丙胺、2-乙基己基异丙胺、乙醇丙胺、乙基乙醇胺、N-羟乙基吗啉、氨基丙基二乙醇胺、二甲氨基乙氧基乙醇、二乙醇胺、N-甲基二乙醇胺、单乙醇胺、三乙醇胺、1-氨基-2-丙醇、3-氨基-1-丙醇、二异丙胺、氨基甲基丙二醇、N,N-二甲氨基甲基丙二醇、氨基乙基丙二醇、N,N-二甲氨基乙基丙二醇、异丙胺、2-氨基-1-丁醇、氨基甲基丙醇、氨基二甲基丙醇、N,N-二甲氨基甲基丙醇、异丁醇胺、二异丙醇胺、3-氨基-4-羟基辛烷、2-氨基丁醇、三(羟甲基)氨基甲烷(TRIS)、N,N-二甲基三(羟甲基)氨基甲烷、羟丙胺、苄胺、羟乙胺、三(羟乙基)氨基甲烷、二甘醇胺、及其组合。
在一个实施例中,所述二醇醚具有式-(CH2)x-的亚甲基连接基团,其中x为2到6的整数,和任选芳族基团,如苯基。在另一实施例中,所述二醇醚选自二乙二醇单甲醚、三乙二醇单甲醚、二乙二醇单乙醚、三乙二醇单乙醚、乙二醇单丙醚、乙二醇单丁醚、二乙二醇单丁醚(BDG,DEGBE)、三乙二醇单丁醚(TEGBE)、乙二醇单己醚(EGHE)、二乙二醇单己醚(DEGHE)、乙二醇苯醚、二乙二醇苯醚、六乙二醇单苯醚、丙二醇甲醚、二丙二醇甲醚(DPGME)、三丙二醇甲醚(TPGME)、二丙二醇二甲醚、二丙二醇乙醚、丙二醇正丙醚、二丙二醇正丙醚(DPGPE)、三丙二醇正丙醚、丙二醇正丁醚(如DOWANOLTMPnB二醇醚,陶氏公司(Dow,Inc.))、二丙二醇正丁醚、三丙二醇正丁醚、二丙二醇苯醚、丙二醇苯醚(如DOWANOLTMPPh二醇苯醚)。
在一个实施例中,所述pH调节剂为一种类型的碱并且以在使用期间有效增加组合物的pH到所需pH的量。在某些实施例中,所述pH将大于7,或介于约8与14之间,或介于约9与14之间。
所述碱可为可用于控制组合物的pH的任何碱,如所指定,许多不同碱性化合物已知在经调适用于清洁微电子装置衬底表面的清洁溶液(例如,作为CMP后清洁溶液)中使用。碱包括(但不限于)氢氧化钾、氢氧化铵(即,氨水)、和具有式NR1R2R3R4OH的四烷基氢氧化铵,其中R1、R2、R3和R4彼此可相同或不同并且选自氢、直链或支链C1-C6烷基(例如,甲基、乙基、丙基、丁基、戊基和己基)、C1-C6羟烷基(例如,羟甲基、羟乙基、羟丙基、羟丁基、羟戊基、和羟己基)和经取代或未经取代的C6-C10芳基(例如,苄基)。碱性化合物的非限制性实例包括:氢氧化胆碱、四丁基氢氧化鏻(TBPH)、四甲基氢氧化鏻、四乙基氢氧化鏻、四丙基氢氧化鏻、苄基三苯基氢氧化鏻、甲基三苯基氢氧化鏻、乙基三苯基氢氧化鏻、N-丙基三苯基氢氧化鏻、四乙基氢氧化铵(TEAH)、四丙基氢氧化铵(TPAH)、四丁基氢氧化铵(TBAH)、三甲基乙基氢氧化铵、二乙基二甲基氢氧化铵、三丁基甲基氢氧化铵(TBMAH)、苄基三甲基氢氧化铵(BTMAH)、四甲基盐酸铵(TMAH)、三(2-羟乙基)甲基氢氧化铵、二乙基二甲基氢氧化铵、乙酸胍、氢氧化铵、1,1,3,3-四甲基胍、碳酸胍、精氨酸、氢氧化钾、氢氧化铯及其组合。
或者或此外,所述pH调节剂可为具有式(PR5R6R7R8)OH的化合物,其中R5、R6、R7和R8彼此可相同或不同并且选自氢、直链C1-C6烷基(例如,甲基、乙基、丙基、丁基、戊基和己基)、支链C1-C6烷基、C1-C6羟烷基(例如,羟甲基、羟乙基、羟丙基、羟丁基、羟戊基、和羟己基)、经取代的C6-C10芳基、未经取代的C6-C10芳基(例如,苄基)及其任何组合,如四丁基氢氧化鏻(TBPH)、四甲基氢氧化鏻、四乙基氢氧化鏻、四丙基氢氧化鏻、苄基三苯基氢氧化鏻、甲基三苯基氢氧化鏻、乙基三苯基氢氧化鏻、N-丙基三苯基氢氧化鏻。
在另一实施例中,pH调节剂(即,碱)选自氢氧化胆碱和四乙基氢氧化铵(TEAH)。
这些碱性化合物可作为组合物中的唯一碱性化合物分开(例如,单独)包含;在组合物中彼此组合,即,作为组合物中的仅两种碱性化合物;或与组合物中的一或多种另外(例如,第二)碱组合。
如本文中所用,术语“表面活性疏水性酸”对应于具有疏水性基团的酸物质,如由本领域技术人员容易理解,但是不包括聚合物表面活性剂。用于本文中所述组合物的示例性表面活性疏水性酸或盐包括十二烷基硫酸钠(SDS)、癸基膦酸、十二烷基膦酸、十四烷基膦酸、十六烷基膦酸、双(2-乙基己基)磷酸盐、十八烷基膦酸、全氟庚酸、全氟癸酸、三氟甲磺酸、膦酰乙酸、十二烷基苯磺酸、经基团R’取代的其它苯磺酸或其盐(其中R’为直链或支链C8-C18烷基)、肉豆蔻基磺酸、十三烷基磺酸、月桂基磺酸、癸基磺酸、十一烷基磺酸、十二烯基琥珀酸、二-(十八烷基)磷酸氢盐、十八烷基磷酸二氢盐、十二烯基琥珀酸、月桂酸、丁酸、戊酸、己酸、庚酸、棕榈酸、油酸、杜松酸、12-羟基硬脂酸、月桂基肌氨酸钠、C1-C6烷基芳基磷酸盐、十八烷基膦酸、十二烷基磷酸盐、月桂基硫酸钠、月桂基硫酸铵、月桂基硫酸钾、双(2-乙基己基)磺基琥珀酸盐、月桂基肌氨酸钠、烷基芳基磷酸盐、硬脂酰基肌氨酸、硬脂酸、花生酸(C20H40O2)、山嵛酸(C22H44O2)、癸酸(C10H20O2)、2-乙基己酸(C8H16O2)、十七酸(C17H34O2)、庚酸(C7H14O2)、三十七酸(C37H74O2)、己酸(C6H12O2)、三十六酸(C36H72O2)、月桂酸(C12H24O2)、三十酸(C30H60O2)、13-甲基十四酸(C15H30O2)、二十八酸(C28H56O2)、肉豆蔻酸(C14H28O2)、新癸酸(C10H20O2)、二十九酸(C29H58O2)、十九酸(CH3(CH2)17COOH)、壬酸(C9H18O2)、棕榈酸(C16H32O2)、二十五酸(C25H50O2)、十五酸(C15H30O2)、植烷酸(C20H40O2)、叶虱酸(C33H66O2)、硬脂酸(C18H36O2)、三十四酸(C34H68O2)、二十三酸(C23H46O2)、十三酸(C13H26O2)、结核菌硬脂酸(C19H38O2)、十一酸(C11H22O2)、辛酸、癸二酸和辛二酸。
在一个实施例中,所述表面活性疏水性酸选自辛酸、十二烷基苯磺酸和壬酸。
在一个实施例中,所述组合物进一步包含腐蚀抑制剂。说明性腐蚀抑制剂包括(但不限于)亚磷酸、次磷酸、亚硫酸、二乙基羟胺、羟胺硫酸盐、偏亚硫酸氢钠、偏亚硫酸氢钾、偏亚硫酸氢铵;选自N-烷基-N-苄基-N,N-二甲基氯化铵和4-(3-苯基丙基)吡啶的季铵盐表面活性剂;乙酸、丙酮肟、丙烯酸、己二酸、丙氨酸、精氨酸、天冬酰胺、天冬氨酸、甜菜碱、二甲基乙二肟、甲酸、富马酸、葡糖酸、谷氨酸、谷胺酰胺、戊二酸、甘油酸、乙醇酸、乙醛酸、组氨酸、亚氨基二乙酸、异酞酸、衣康酸、乳酸、亮氨酸、赖氨酸、马来酸、马来酸酐、苹果酸、丙二酸、扁桃酸、2,4-戊二酮、苯基乙酸、苯丙氨酸、酞酸、脯氨酸、丙酸、邻苯二酚、均苯四甲酸、奎尼酸、丝氨酸、琥珀酸、酒石酸、对苯二甲酸、偏苯三甲酸、均苯三甲酸、酪氨酸、缬氨酸、木糖醇、草酸、单宁酸、吡啶甲酸、1,3-环戊烷二酮、儿茶酚、焦棓酚、间苯二酚、氢醌、氰尿酸、巴比妥酸、1,2-二甲基巴比妥酸、丙酮酸、丙硫醇、苯甲羟肟酸、2,5-二羧基吡啶、4-(2-羟乙基)吗啉(HEM)、N-氨基乙基哌嗪(N-AEP)、乙二胺四乙酸(EDTA)、1,2-环己二胺-N,N,N',N'-四乙酸(CDTA)、N-(羟乙基)-乙二胺三乙酸(HEdTA)、亚氨基二乙酸(IDA)、2-(羟乙基)亚氨基二乙酸(HIDA)、次氮基三乙酸、硫脲、1,1,3,3-四甲基脲、脲、脲衍生物、甘氨酸、半胱氨酸、谷氨酸、异亮氨酸、甲硫氨酸、哌啶、N-(2-氨基乙基)哌啶、吡咯烷、苏氨酸、色氨酸、水杨酸、对甲苯磺酸、水杨基羟肟酸、5-磺基水杨酸、三唑、氨基三唑、二甲基炔丙醇、糖精及其组合。
在另一实施例中,所述腐蚀抑制剂为用作还原剂的化合物。示例性化合物包括(但不限于)抗坏血酸、L(+)-抗坏血酸、异抗坏血酸、抗坏血酸衍生物、亚硫酸、亚硫酸铵、亚硫酸钾、亚硫酸钠、多巴胺HCl、亚磷酸、次膦酸、次磷酸、偏亚硫酸氢钾、偏亚硫酸氢钠、偏亚硫酸氢铵、丙酮酸钾、丙酮酸钠、丙酮酸铵、甲酸、甲酸钠、甲酸钾、甲酸铵、多巴胺、二氧化硫溶液及其任何组合。例如,所述腐蚀抑制剂/还原剂可包含至少一个亚硫酸根离子和至少一种其它所列举的还原剂,例如,亚硫酸、亚硫酸钾、亚硫酸铵、次膦酸、二乙基羟胺硫酸盐、二乙基羟胺磷酸盐及其任何组合。应理解,当存在亚硫酸铵时,所述亚硫酸铵可原位产生,其中特定组分的组合导致亚硫酸铵的形成以帮助移除残留物。
在另一实施例中,所述腐蚀抑制剂选自抗坏血酸、亚磷酸、次磷酸、亚硫酸、二乙基羟胺、羟胺硫酸盐、偏亚硫酸氢钠/铵/钾和亚硫酸钠/铵/钾和季铵盐表面活性剂,包括N-烷基-N-苄基-N,N-二甲基氯化铵(苯扎氯铵)和4-(3-苯基丙基)吡啶。
于各种实施例中,当存在时,组合物中的腐蚀抑制剂的量在基于组合物的总重量计约0.0001重量%到约1重量%的范围内。在另一实施例中,所述还原剂以基于组合物的总重量计约0.0001重量%到约0.2重量%的量存在,和在另一实施例中,以约0.01重量%到约0.2重量%的量存在。在某些实施例中,所述清洁组合物不含有腐蚀抑制剂/还原剂。
在其它实施例中,所述组合物包含功能为氢键结添加剂的化合物,所述添加剂用于减少二氧化硅粒子粘到在CMP后微电子装置的清洁中所利用的刷子。参见,例如,美国专利公开第2019/0168265号,其以引用的方式并入本文中。示例性化合物包括非离子、阴离子、阳离子和两性离子小分子和可在中性pH下表现为聚电解质的聚合物。阴离子聚合物或阴离子聚电解质可为天然聚合物、改性天然聚合物或合成聚合物。可包含于组合物中的示例性天然和改性天然阴离子聚合物包括(但不限于)藻酸(或盐)、羧甲基纤维素、硫酸葡聚糖、聚(半乳糖醛酸)及其盐。示例性合成阴离子聚电解质包括(但不限于):(甲基)丙烯酸(或盐)、聚(丙烯酸)、马来酸(或酸酐)、苯乙烯磺酸(或盐)、乙烯基磺酸(或盐)、烯丙基磺酸(或盐)、丙烯酰胺基丙基磺酸(或盐)等等的均聚物或共聚物,其中羧酸和磺酸的盐优选经铵或烷基铵阳离子中和。在一个实施例中,聚电解质阴离子聚合物的阳离子为铵阳离子(NH4 +)、胆碱鎓+N(CH3)3(CH2CH2OH)和+N(CH3)4。因此,组合的合成和天然聚电解质阴离子聚合物的实例为(甲基)丙烯酸、马来酸(或酸酐)、苯乙烯磺酸、乙烯基磺酸、烯丙基磺酸、乙烯基膦酸、丙烯酰胺基丙基磺酸、藻酸、羧甲基纤维素、硫酸葡聚糖、聚(半乳糖醛酸)及其盐的均聚物或共聚物。
阳离子聚合物和阳离子聚电解质可为天然聚合物、改性天然聚合物或合成聚合物。示例性天然和改性天然阳离子聚合物包括(但不限于):壳聚糖、阳离子淀粉、聚赖氨酸及其盐。示例性阳离子合成聚电解质包括(但不限于):二烯丙基二甲基氯化铵(DADMAC)、二烯丙基二甲基溴化铵、二烯丙基二甲基硫酸铵、二烯丙基二甲基膦酸铵、二甲基烯丙基二甲基氯化铵、二乙基烯丙基二甲基氯化铵、二烯丙基二(β-羟乙基)氯化铵、二烯丙基二(β-乙氧基乙基)氯化铵、(甲基)丙烯酸二甲氨基乙酯酸加成盐和季铵盐、(甲基)丙烯酸二乙氨基乙酯酸加成盐和季铵盐、(甲基)丙烯酸7-氨基-3,7-二甲基辛酯酸加成盐和季铵盐、N,N'-二甲氨基丙基丙烯酰胺酸加成盐和季铵盐(其中所述季铵盐包括烷基和苄基季铵化的盐)、烯丙胺、二烯丙胺、乙烯胺(通过乙烯基烷基酰胺聚合物的水解获得)、乙烯基吡啶、壳聚糖、阳离子淀粉、聚赖氨酸及其盐的均聚物或共聚物。
其它实例包括2-吡咯烷酮、1-(2-羟乙基)-2-吡咯烷酮(HEP)、甘油、1,4-丁二醇、四亚甲基砜(环丁砜)、二甲基砜、乙二醇、丙二醇、二丙二醇、四乙二醇二甲醚和二乙二醇二甲醚。
或者,或此外,所述氢键结添加剂包括羟丙基纤维素、羟乙基纤维素、羟乙基甲基纤维素、羟丙基甲基纤维素、羧甲基纤维素、羧甲基纤维素钠、聚乙烯吡咯烷酮(PVP)、使用N-乙烯基吡咯烷酮单体制得的任何聚合物、聚丙烯酸酯和聚丙烯酸酯的类似物、聚氨基酸(例如,聚丙氨酸、聚亮氨酸、聚甘氨酸)、聚酰胺基羟基氨基甲酸酯、聚内酯、聚丙烯酰胺、黄原胶、壳聚糖、聚环氧乙烷、聚乙烯醇(PVA)、聚乙酸乙烯酯、聚丙烯酸、聚乙烯亚胺、糖醇(如山梨醇、蔗糖、果糖、乳糖、半乳糖、麦芽糖、赤藓糖醇、麦芽糖醇、苏糖醇、阿拉伯糖醇、核糖醇、甘露醇、半乳糖醇、肌醇和木糖醇)、脱水山梨糖醇的酯、二级醇乙氧基化物(如TERGITOLTM表面活性剂)、多官能基醇(包括新戊四醇、二新戊四醇、三羟甲基丙烷、二甲基丙酸和木糖酸)、核碱基(如尿嘧啶、胞嘧啶、鸟嘌呤、胸腺嘌呤)及其组合。
氢键结添加剂的还有其它实例包括乳酸、马来酸、脲、乙醇酸、山梨醇、硼砂(即,硼酸钠)、脯氨酸、甜菜碱、甘氨酸、组氨酸、TRIS(三(羟甲基)氨基甲烷)、二甲亚砜、环丁砜、甘油、SDS(十二烷基硫酸钠)、十二烷基膦酸或其组合。在这些中的一者中,某些粒子移除剂可优选用于微电子装置衬底的CMP后清洁步骤中,例如:马来酸、硼砂(即,硼酸钠)、二甲亚砜、甘油或其组合。当存在时,这些添加剂将以约0.0001到15重量%,或约0.001到约10重量%,约1到约10重量%,或约1到约9重量%存在。
在一个实施例中,所述组合物进一步包含络合剂。一般而言,用于CMP后清洁组合物中的络合剂为通常与金属离子(通常铁离子)形成络合物分子以使清洁溶液中的铁失活和防止铁的化学反应或活性的化学化合物。用于CMP后清洁组合物中的各种络合剂是已知且可用于本描述的清洁组合物和方法中。某些特定实例包括含酸有机分子,尤其含羧酸有机分子,如直链或支链C1-C6羧酸化合物,其包括酞酸、琥珀酸、柠檬酸、酒石酸、苹果酸、葡糖酸、天冬氨酸或其组合,以及甘氨酸、氨基酸等等。柠檬酸可为用于络合铁离子(例如,Fe+2、Fe+3)的优选络合剂。在某些实施例中,利用糖醇,如:阿拉伯醇、赤藓糖醇、甘油、氢化淀粉水解产物(HSH)、异麦芽酮糖醇、乳糖醇、麦芽糖醇、甘露醇、山梨醇和木糖醇作为金属离子的络合试剂。
本文中设想的其它金属络合试剂包括(但不限于)乙酸、丙酮肟、丙烯酸、己二酸、丙氨酸、精氨酸、天冬酰胺、天冬氨酸、甜菜碱、二甲基乙二肟、甲酸、富马酸、葡糖酸、谷氨酸、谷胺酰胺、戊二酸、甘油酸、甘油、乙醇酸、乙醛酸、组氨酸、亚氨基二乙酸、异酞酸、衣康酸、乳酸、亮氨酸、赖氨酸、马来酸、马来酸酐、苹果酸、丙二酸、扁桃酸、2,4-戊二酮、苯基乙酸、苯丙氨酸、酞酸、脯氨酸、丙酸、邻苯二酚、均苯四甲酸、奎尼酸、丝氨酸、山梨醇、琥珀酸、酒石酸、对苯二甲酸、偏苯三甲酸、均苯三甲酸、酪氨酸、缬氨酸、木糖醇、乙二胺、草酸、单宁酸、吡啶甲酸、1,3-环戊烷二酮、儿茶酚、焦棓酚、间苯二酚、氢醌、氰尿酸、巴比妥酸、1,2-二甲基巴比妥酸、丙酮酸、丙硫醇、苯甲羟肟酸、四亚乙基五胺(TEPA)、4-(2-羟乙基)吗啉(HEM)、N-氨基乙基哌嗪(N-AEP)、乙二胺四乙酸(EDTA)、1,2-环己二胺-N,N,N',N'-四乙酸(CDTA)、N-(羟乙基)-乙二胺三乙酸(HEdTA)、亚氨基二乙酸(IDA)、2-(羟乙基)亚氨基二乙酸(HIDA)、次氮基三乙酸、氨基三(亚甲基膦酸)、羟基次乙基二膦酸、乙二胺四(亚甲基膦酸)、乙二胺五(亚甲基膦酸)、硫脲、1,1,3,3-四甲基脲、脲、脲衍生物、甘氨酸、半胱氨酸、谷氨酸、异亮氨酸、甲硫氨酸、哌啶、N-(2-氨基乙基)哌啶、吡咯烷、苏氨酸、色氨酸、水杨酸、吡啶二甲酸、对甲苯磺酸、5-磺基水杨酸及其组合。
可用络合剂的其它实例包括衍生自单体的含羧酸基团寡聚物和聚合物,所述单体可包括丙烯酸、甲基丙烯酸、马来酸、琥珀酸、天冬氨酸、2-丙烯酰胺基-2-甲基-1-丙磺酸、丙烯酰胺、膦酸甲基丙烯酰胺基丙基三甲基氯化铵、烯丙基卤化物中的一或多者;或其组合。聚丙烯酸可为用于络合氮化硅(SiN)的优选络合剂。还有其它实例包括:丙烷-1,2,3-三甲酸、丁烷-1,2,3,4-四甲酸、戊烷-1,2,3,4,5-五甲酸、偏苯三甲酸、均苯三甲酸、均苯四甲酸、苯六甲酸及其组合。
一般而言,络合剂可以一定量包含于清洁溶液中,所述量可用于以本文中所述方式有效用于络合剂。包含于给定清洁溶液中的络合剂的特定类型和量可基于包含以下的因素选择:正在清洁的衬底的类型、存在于衬底表面上的残留物的类型、清洁溶液中的其它成分和CMP后清洁工艺的条件。当存在时,所述络合剂以约0.5到约20重量%、约0.5到约10重量%或约0.8到约6重量%利用。
本发明的清洁组合物可进一步包含其它成分或佐剂(包括聚合物和表面活性剂)以改良使用所述清洁溶液的CMP后清洁步骤的清洁效应或效率。这些成分包括表面活性剂和杀生物剂。
示例性表面活性剂和聚合物包括阴离子、非离子、阳离子和/或两性离子表面活性剂。当存在时,这些表面活性剂和聚合物将以约0.0001到约10重量%的量存在。实例包括藻酸及其盐;羟基或羧基烷基纤维素;硫酸葡聚糖及其盐;聚(半乳糖醛酸)及其盐;(甲基)丙烯酸及其盐、马来酸、马来酸酐、苯乙烯磺酸及其盐、乙烯基磺酸及其盐、烯丙基磺酸及其盐、丙烯酰胺基丙基磺酸及其盐的均聚物;(甲基)丙烯酸及其盐、马来酸、马来酸酐、苯乙烯磺酸及其盐、乙烯基磺酸及其盐、烯丙基磺酸及其盐、丙烯酰胺基丙基磺酸及其盐的共聚物;壳聚糖;阳离子淀粉;聚赖氨酸及其盐;二烯丙基二甲基氯化铵(DADMAC)、二烯丙基二甲基溴化铵、二烯丙基二甲基硫酸铵、二烯丙基二甲基膦酸铵、二甲基烯丙基二甲基氯化铵、二乙基烯丙基二甲基氯化铵、二烯丙基二(β-羟乙基)氯化铵、二烯丙基二(β-乙氧基乙基)氯化铵、(甲基)丙烯酸二甲氨基乙酯酸加成盐和季铵盐、(甲基)丙烯酸二乙氨基乙酯酸加成盐和季铵盐、(甲基)丙烯酸7-氨基-3,7-二甲基辛酯酸加成盐和季铵盐、N,N'-二甲氨基丙基丙烯酰胺酸加成盐和季铵盐、烯丙胺、二烯丙胺、乙烯胺、乙烯基吡啶的均聚物;和二烯丙基二甲基氯化铵(DADMAC)、二烯丙基二甲基溴化铵、二烯丙基二甲基硫酸铵、二烯丙基二甲基膦酸铵、二甲基烯丙基二甲基氯化铵、二乙基烯丙基二甲基氯化铵、二烯丙基二(β-羟乙基)氯化铵、二烯丙基二(β-乙氧基乙基)氯化铵、(甲基)丙烯酸二甲氨基乙酯酸加成盐和季铵盐、(甲基)丙烯酸二乙氨基乙酯酸加成盐和季铵盐、(甲基)丙烯酸7-氨基-3,7-二甲基辛酯酸加成盐和季铵盐、N,N'-二甲氨基丙基丙烯酰胺酸加成盐和季铵盐、烯丙胺、二烯丙胺、乙烯胺、乙烯基吡啶的共聚物;椰油基二甲基羧甲基甜菜碱;月桂基二甲基羧甲基甜菜碱;月桂基二甲基-α-羧乙基甜菜碱;鲸蜡基二甲基羧甲基甜菜碱;月桂基-双(2-羟乙基)羧甲基甜菜碱;硬脂酰基-双(2-羟丙基)羧甲基甜菜碱;油烯基二甲基-γ-羧丙基甜菜碱;月桂基-双(2-羟丙基)α-羧乙基甜菜碱;椰油基二甲基磺丙基甜菜碱;硬脂酰基二甲基磺丙基甜菜碱;月桂基-双(2-羟乙基)磺丙基甜菜碱;Surfynol 104(及其乙氧基化衍生物);二辛基磺基琥珀酸钠盐;月桂基醚硫酸钠;支链聚乙二醇-壬基苯基醚硫酸铵盐;2-十二烷基-3-(2-磺酸根基苯氧基)二钠;PEG25-PABA;聚乙二醇单C10-16烷基醚硫酸钠盐;(2-N-丁氧乙氧基)乙酸;十六烷基苯磺酸;鲸蜡基三甲基氢氧化铵;十二烷基三甲基氢氧化铵;十二烷基三甲基氯化铵;鲸蜡基三甲基氯化铵;N-烷基-N-苄基-N,N-二甲基氯化铵;十二烷胺;聚氧乙烯月桂基醚;十二烯基琥珀酸单二乙醇酰胺;乙二胺四(乙氧基化物-嵌段-丙氧基化物);及其组合。
在另一实施例中,所述组合物进一步包含水溶性或水可分散性聚合物。当存在时,这些聚合物包括(但不限于)甲基丙烯酸均聚物和与丙烯酰胺基甲基丙磺酸和马来酸的共聚物;马来酸/乙烯基醚共聚物;聚(乙烯基吡咯烷酮)/乙酸乙烯酯;膦酸化聚乙二醇寡聚物、聚(丙烯酸)、聚(丙烯酰胺)、聚(乙酸乙烯酯)、聚(乙二醇)、聚(丙二醇)、聚(苯乙烯磺酸)、聚(乙烯基磺酸)、聚(乙烯基膦酸)、聚(乙烯基磷酸)、聚(乙烯亚胺)、聚(丙烯亚胺)、聚烯丙胺、聚环氧乙烷、聚乙烯基吡咯烷酮、PPG-PEG-PPG嵌段共聚物、PEG-PPG-PEG嵌段共聚物、聚(乙烯醇)、聚丙烯酸(羟乙基)酯、聚甲基丙烯酸(羟乙基)酯、羟乙基纤维素、甲基羟乙基纤维素、羟丙基纤维素、甲基羟丙基纤维素、黄原胶、藻酸钾、果胶、羧甲基纤维素、葡糖胺、聚(二烯丙基二甲基铵)氯化物、聚(2-丙烯酰胺基-2-甲基-1-丙磺酸)、聚(苯乙烯磺酸)、聚乙烯基吡咯烷酮、PVA-聚(2-丙烯酰胺基-2-甲基-1-丙磺酸)共聚物、聚乙二醇化甲基丙烯酸酯/丙烯酸酯共聚物、聚(2-甲基丙烯酰氧基乙基三甲基氯化铵)CAS号26161-33-1及其共聚物、二甲氨基甲基丙烯酸酯聚合物及其共聚物、三甲基铵甲基丙烯酸甲酯聚合物及其共聚物、二甲氨基甲基丙烯酸酯聚合物及其共聚物、三甲基铵甲基丙烯酸甲酯聚合物及其共聚物、及其组合。以上共聚物可为无规或嵌段共聚物。当存在时,聚合物在组合物中的量在基于所述组合物的总重量计约0.0001重量%到约5重量%的范围内。
本文中设想的示例性杀生物剂包括(但不限于)异噻唑啉酮杀生物剂,如5-氯-2-甲基-4-异噻唑啉-3-酮、2-甲基-4-异噻唑啉-3-酮、苯并异噻唑酮、1,2-苯并异噻唑-3[2H]-酮、甲基异噻唑啉酮、甲基氯异噻唑啉酮及其组合。在一个实施例中,杀生物剂可包括。杀生物剂的一个实例为GXL(BIT)1,2-苯并异噻唑-3(2H)-酮。
在某些实施例中,组合物的组分以下列比例存在:
a.60到80重量%的水,例如,去离子水;
b.0.1到20重量%的具有2到7个碳原子的烷醇胺;或0.1到10重量%,或1到6重量%;
c.0.01到30重量%的二醇醚;或1到15重量%,或1到10重量%;
d.0.001到10重量%的pH调节剂;
e.0.00001到10重量%,或0.0001到8重量%,或0.005到5重量%的表面活性疏水性酸,其中a.、b.、c.、d.和e.总计为100%。
pH调节剂的量取决于当制备移除组合物供使用时寻求的最终pH,基于本文中所公开的pH值和本领域技术人员的知识。在某些实施例中,所述pH将大于7,或介于约8与14之间,或介于约9与14之间。
组分的重量%比率的范围将覆盖组合物的所有可能浓缩或稀释实施例。为此,在一个实施例中,提供浓缩组合物,可将其稀释用作清洁溶液。浓缩组合物,或"浓缩物"有利地允许使用者(例如,CMP工艺工程师)将浓缩物在使用点时稀释到所需强度和pH。浓缩含水移除组合物的稀释可在约1:1到约2500:1,约5:1到约200:1,或约20:1到约120:1的范围内,其中将所述含水移除组合物在使用工具时或就在使用工具之前用溶剂(例如,去离子水)稀释。本领域技术人员应理解,在稀释后,本文中所公开组分的重量%比率的范围应保持不变。
根据某些实例,在稀释到使用点组合物之前,清洁溶液呈浓缩形式,在某些实施例中,所述组合物可为至多20%,或0.5到10%,或0.8到6%的范围的浓缩物。
本文中所述组合物可在应用中具有效用,所述应用包括(但不限于)蚀刻后残留物移除、灰化后残留物移除表面制备、电镀后清洁和CMP后残留物移除。此外,考虑的是本文中所述的清洁组合物可用于清洁和保护其它金属(例如,含铜、含钨、含钌、含钴)产品,包括(但不限于)装饰性金属、金属丝焊接、印刷电路板和使用金属或金属合金,连同电介质材料(如等离子体增强的原硅酸四乙酯(PETEOS)、氮化硅、氧氮化硅、碳化硅、CVD碳、多孔有机硅酸盐玻璃、CSOD、类金刚石碳、倍半硅氧烷基电介质(如氢倍半硅氧烷(HSQ)和甲基倍半硅氧烷(MSQ))、硅、BPSG和HDP)的其它电子包装。
所述移除组合物容易通过简单添加相应成分和混合到均匀条件来配制。此外,所述组合物可容易呈单包装制剂或在使用点时或在使用点之前混合的多部分制剂配制,例如,多部分制剂的个别部分可在使用工具时或在工具的储存槽上游混合。相应成分的浓度可在特定倍数的组合物(即,更稀释或更浓缩)中广泛变化,并且应理解,本文中所述组合物可各种和或者包含与本文中公开内容一致的成分的任何组合,由其组成或基本上由其组成。
因此,另一方面涉及包含一或多个容器的试剂盒,所述容器中具有适用于移除的组分。一种包含一或多个容器的试剂盒,所述容器中具有适用于自其上具有二氧化铈粒子和化学机械抛光污染物的微电子装置移除所述粒子和污染物的组分,其中所述试剂盒的一或多个容器包含组合物,所述组合物包含:
a.水;
b.具有2到7个碳原子的烷醇胺;
c.二醇醚;
d.pH调节剂;和
e.表面活性疏水性酸。
试剂盒的容器必须适用于储存和船运组合物并且可为(例如)容器(美国马萨诸塞州比勒里卡的应特格公司(Entegris,Inc.,Billerica,Mass.,USA))。
在一个实施例中,含有组合物的组分的一或多个容器包含将所述一或多个容器中的组分处于流体连通供共混和分配的装置。例如,提及容器,可将气压施加到所述一或多个容器的内衬外部以引起内衬的内容物的至少一部分排出和因此使能流体连通供共混和分配用。或者,可将气压施加到常规可加压容器的头部空间或可使用泵使能流体连通。此外,在某些实施例中,系统包含用于将经共混的移除组合物分配给加工工具的分配端口。
如应用于微电子制造操作,可用地采用本文中所述的移除组合物以自微电子装置表面清洁残留物和/或CMP污染物(例如,CMP后残留物和污染物)。所述移除组合物不损伤装置表面上的低k电介质材料(例如,氧化硅)、氮化硅层或含钨层。在一个实施例中,含水移除组合物移除至少85%,至少90%、至少95%或至少99%的在粒子移除之前存在于装置上的磨料粒子。
因此,在另一方面,本发明提供一种自其上具有残留物和/或污染物的微电子装置移除所述残留物和污染物的方法,所述方法包括:(i)使所述微电子装置与本发明的组合物接触;和(ii)自所述微电子装置至少部分移除所述粒子和污染物,其中所述微电子装置包含选自含铜、含钨、含钌、含钴产品的衬底,所述产品包括(但不限于)装饰性金属、金属丝焊接、印刷电路板和使用金属或金属合金,连同电介质材料(如等离子体增强的原硅酸四乙酯(PETEOS)、氮化硅、氧氮化硅、碳化硅、CVD碳、多孔有机硅酸盐玻璃、CSOD、类金刚石碳、倍半硅氧烷基电介质(如氢倍半硅氧烷(HSQ)和甲基倍半硅氧烷(MSQ))、硅、BPSG和HDP)的其它电子包装。
在CMP后粒子和污染物移除应用中,本文中所述的含水移除组合物可使用各种常规清洁工具,如超高频音波和刷子擦洗,包括(但不限于)维特克公司(Verteq)的单晶圆超高频音波Goldfinger、OnTrak系统DDS(双面洗涤器)、SEZ或其它单晶圆喷雾冲洗、应用材料公司(Applied Materials)的Mirra-MesaTM/ReflexionTM/Reflexion LKTM、超高频音波分批湿式工作台系统、荏原技术公司(EBARA Technologies,Inc.)的300mm型号(FREX300S2和FREX300X3SC)和200mm CMP系统(FREX200M)。
在使用本文中所述组合物用于自其上具有残留物和/或污染物的微电子装置移除所述残留物和/或污染物中,所述含水移除组合物通常在约20℃到约90℃,或约20℃到约50℃范围的温度下与所述装置接触约5秒到约10分钟,或约1秒到20分钟,或约15秒到约5分钟的时间。这些接触时间和温度为说明性,并且可在方法的广泛实践中采用对自装置至少部分移除残留物和/或污染物有效的任何其它适宜时间和温度条件。在某些实施例中,"至少部分清洁"和"实质上移除"均对应于移除至少85%,至少90%、至少95%或至少99%的在粒子移除之前存在于装置上的残留物和/或污染物。
在达成所需粒子移除作用后,所述含水移除组合物可容易自先前施覆其的装置移除,如可在本文中所述组合物的给定最终用途应用中所需且有效。在一个实施例中,所述冲洗溶液包含去离子水。之后,可将装置使用氮气或旋干循环干燥。
又一方面涉及根据本文中所述方法制备的改良的微电子装置和含有这些微电子装置的产品。
另一方面涉及再循环的含水移除组合物,其中所述移除组合物可经再循环直到残留物和/或污染物负载达到含水移除组合物可容纳的最大量,如由本领域技术人员容易测定。
还有另一方面涉及使用本文中所述组合物制造包含微电子装置的制品的方法,所述方法包括使所述微电子装置与本发明的组合物接触足够时间以自其上具有残留物和/或污染物的微电子装置移除所述残留物和/或污染物,和将所述微电子装置并入所述制品中。
本发明可通过其优选实施例的下列实例进一步说明,但是应理解,除非另有明确指定,否则这些实例仅出于说明目的包含且不意欲限制本发明的范围。
实例
参考图1,制备样品1、2、3和4并使其经受对PETEOS的烧杯浸渍试验。一般而言,所述程序涉及将测试晶圆在室温下利用磁性搅拌棒在100rpm下暴露于受污染浆液中约5分钟。接下来,将晶圆在室温下利用磁性搅拌棒在550rpm下放入本发明的组合物中约30秒。然后将晶圆在第三个烧杯中用去离子水冲洗约20秒,接着用干燥氮气吹干。在浸渍试验后,将晶圆样品通过SEM测量值和粒子计数程序经筛选以按基于数字的图转换和比较清洁性能。
如图1中所示,其中样品1用作比较例,本发明的组合物显示显著残留物移除结果。
样品1
样品2:
样品3与实例2相同,不同之处在于省略4-十二烷基苯磺酸。
样品4与实例2相同,不同之处在于省略乙二醇单己醚。
图2为样品1(比较例)和改良的制剂的表面张力和水接触角(WCA)。样品2的新近引入的表面活性疏水性酸说明表面张力的降低帮助晶圆的清洁效应。
样品X系列:
*表面活性添加剂 | CAS号 | 清洁剂样品编号 |
丁酸 | 107-92-6 | 样品X BA |
辛酸 | 124-07-2 | 样品X OA |
壬酸 | 112-05-0 | 样品X NA |
癸酸 | 334-48-5 | 样品X DA |
癸二酸 | 111-20-6 | 样品X SA |
辛二酸 | 505-48-6 | 样品X SBA |
柠檬酸–(比较例) | 77-92-9 | 样品X CA |
图3为各种表面活性添加剂系列的粒子面积结果用于比较制剂的清洁效应。各制剂具有表面活性添加剂的不同特征(如官能基的烷基链长度或数目)以发现用于清洁晶圆的最有效结构。样品X OA和样品X NA显示最好结果。
本发明已特别参考其某些实施例进行详细描述,但是应理解,变化和修改可在本发明的精神和范围内实现。
Claims (20)
1.一种组合物,其包含:
a.水;
b.具有2到7个碳原子的烷醇胺;
c.二醇醚;
d.pH调节剂;和
e.表面活性疏水性酸。
2.根据权利要求1所述的组合物,其中所述烷醇胺选自氨基乙基乙醇胺、N-甲氨基乙醇、氨基乙氧基乙醇、氨基乙氧基乙氧基乙醇、甲氧基丙胺、丁氧基异丙胺、2-乙基己基异丙氧胺、乙醇丙胺、乙基乙醇胺、N-羟乙基吗啉、氨基丙基二乙醇胺、二甲氨基乙氧基乙醇、二乙醇胺、N-甲基二乙醇胺、单乙醇胺、三乙醇胺、1-氨基-2-丙醇、3-氨基丙醇、二异丙胺、氨基甲基丙二醇、N,N-二甲氨基甲基丙二醇、氨基乙基丙二醇、N,N-二甲氨基乙基丙二醇、异丙胺、2-氨基-1-丁醇、氨基甲基丙醇、氨基二甲基丙醇、N,N-二甲氨基甲基丙醇、异丁醇胺、二异丙醇胺、3-氨基-4-羟基辛烷、2-氨基丁醇、三(羟甲基)氨基甲烷、N,N-二甲基三(羟甲基)氨基甲烷、羟丙胺、苄胺、羟乙胺、三(羟乙基)氨基甲烷、二甘醇胺、及其组合。
3.根据权利要求2所述的组合物,其中所述烷醇胺选自单乙醇胺、异丙醇胺和二异丙醇胺。
4.根据权利要求1所述的组合物,其中所述二醇醚具有式-(CH2)x-的亚甲基连接基团,其中x为2到6的整数。
5.根据权利要求1所述的组合物,其中所述二醇醚选自二乙二醇单甲醚、三乙二醇单甲醚、二乙二醇单乙醚、三乙二醇单乙醚、乙二醇单丙醚、乙二醇单丁醚、二乙二醇单丁醚、三乙二醇单丁醚、乙二醇单己醚、二乙二醇单己醚、乙二醇苯醚、二乙二醇苯醚、六乙二醇单苯醚、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、三丙二醇正丁醚和二丙二醇苯醚、丙二醇苯醚。
6.根据权利要求5所述的组合物,其中所述二醇醚选自三乙二醇单丁醚、二乙二醇单丁醚、乙二醇单丁醚、三乙二醇单己醚、二乙二醇单己醚、和乙二醇单己醚。
7.根据权利要求5所述的组合物,其中所述二醇醚为乙二醇单己醚。
8.根据权利要求1所述的组合物,其中所述pH调节剂选自氢氧化胆碱和四乙基氢氧化铵。
9.根据权利要求1所述的组合物,其中所述表面活性疏水性酸选自十二烷基硫酸钠、癸基膦酸、十二烷基膦酸、十四烷基膦酸、十六烷基膦酸、双(2-乙基己基)磷酸盐、十八烷基膦酸、全氟庚酸、全氟癸酸、三氟甲磺酸、膦酰乙酸、十二烷基苯磺酸、经基团R’取代的其它苯磺酸或其盐(其中R’为直链或支链C8-C18烷基)、肉豆蔻基磺酸、十三烷基磺酸、月桂基磺酸、癸基磺酸、十一烷基磺酸、十二烯基琥珀酸、二-(十八烷基)磷酸氢盐、十八烷基磷酸二氢盐、十二烯基琥珀酸、月桂酸、丁酸、戊酸、己酸、庚酸、棕榈酸、油酸、杜松酸、12-羟基硬脂酸、月桂基肌氨酸钠、C1-C6烷基芳基磷酸盐、十八烷基膦酸、十二烷基磷酸盐、月桂基硫酸钠、月桂基硫酸铵、月桂基硫酸钾、双(2-乙基己基)磺基琥珀酸盐、月桂基肌氨酸钠、烷基芳基磷酸盐、硬脂酰基肌氨酸、硬脂酸、花生酸(C20H40O2)、山嵛酸(C22H44O2)、癸酸(C10H20O2)、2-乙基己酸(C8H16O2)、十七酸(C17H34O2)、庚酸(C7H14O2)、三十七酸(C37H74O2)、己酸(C6H12O2)、三十六酸(C36H72O2)、月桂酸(C12H24O2)、三十酸(C30H60O2)、13-甲基十四酸(C15H30O2)、二十八酸(C28H56O2)、肉豆蔻酸(C14H28O2)、新癸酸(C10H20O2)、二十九酸(C29H58O2)、十九酸(CH3(CH2)17COOH)、壬酸(C9H18O2)、棕榈酸(C16H32O2)、二十五酸(C25H50O2)、十五酸(C15H30O2)、植烷酸(C20H40O2)、叶虱酸(C33H66O2)、硬脂酸(C18H36O2)、三十四酸(C34H68O2)、二十三酸(C23H46O2)、十三酸(C13H26O2)、结核菌硬脂酸(C19H38O2)、十一酸(C11H22O2)、辛酸、壬酸、癸酸、癸二酸和辛二酸。
10.根据权利要求1所述的组合物,其进一步包含腐蚀抑制剂。
11.根据权利要求10所述的组合物,其中所述腐蚀抑制剂选自亚磷酸、次磷酸、亚硫酸、二乙基羟胺、羟胺硫酸盐、偏亚硫酸氢钠、偏亚硫酸氢钾、偏亚硫酸氢铵、选自N-烷基-N-苄基-N,N-二甲基氯化铵和4-(3-苯基丙基)吡啶的季铵盐表面活性剂、乙酸、丙酮肟、丙烯酸、己二酸、丙氨酸、精氨酸、天冬酰胺、天冬氨酸、甜菜碱、二甲基乙二肟、甲酸、富马酸、葡糖酸、谷氨酸、谷胺酰胺、戊二酸、甘油酸、乙醇酸、乙醛酸、组氨酸、亚氨基二乙酸、异酞酸、衣康酸、乳酸、亮氨酸、赖氨酸、马来酸、马来酸酐、苹果酸、丙二酸、扁桃酸、2,4-戊二酮、苯基乙酸、苯丙氨酸、酞酸、脯氨酸、丙酸、邻苯二酚、均苯四甲酸、奎尼酸、丝氨酸、琥珀酸、酒石酸、对苯二甲酸、偏苯三甲酸、均苯三甲酸、酪氨酸、缬氨酸、木糖醇、草酸、单宁酸、吡啶甲酸、1,3-环戊烷二酮、儿茶酚、焦棓酚、间苯二酚、氢醌、氰尿酸、巴比妥酸、1,2-二甲基巴比妥酸、丙酮酸、丙硫醇、苯甲羟肟酸、2,5-二羧基吡啶、4-(2-羟乙基)吗啉、N-氨基乙基哌嗪(N-AEP)、乙二胺四乙酸、1,2-环己二胺-N,N,N',N'-四乙酸、N-(羟乙基)-乙二胺三乙酸、亚氨基二乙酸、2-(羟乙基)亚氨基二乙酸、次氮基三乙酸、硫脲、1,1,3,3-四甲基脲、脲、脲衍生物、甘氨酸、半胱氨酸、谷氨酸、异亮氨酸、甲硫氨酸、哌啶、N-(2-氨基乙基)哌啶、吡咯烷、苏氨酸、色氨酸、水杨酸、对甲苯磺酸、水杨基羟肟酸、5-磺基水杨酸、三唑、氨基三唑、二甲基炔丙醇、糖精及其组合。
12.根据权利要求10所述的组合物,其中所述腐蚀抑制剂选自抗坏血酸、L(+)-抗坏血酸、异抗坏血酸、抗坏血酸衍生物、亚硫酸、亚硫酸铵、亚硫酸钾、亚硫酸钠、多巴胺HCl、亚磷酸、次膦酸、次磷酸、偏亚硫酸氢钾、偏亚硫酸氢钠、偏亚硫酸氢铵、丙酮酸钾、丙酮酸钠、丙酮酸铵、甲酸、甲酸钠、甲酸钾、甲酸铵、多巴胺、二氧化硫溶液及其任何组合。例如,所述腐蚀抑制剂/还原剂可包含至少一个亚硫酸根离子和至少一种其它所列举的还原剂,例如,亚硫酸、亚硫酸钾、亚硫酸铵、次膦酸、二乙基羟胺、二乙基羟胺硫酸盐、二乙基羟胺磷酸盐及其任何组合。
13.根据权利要求10所述的组合物,其中所述腐蚀抑制剂选自抗坏血酸、亚磷酸、次磷酸、亚硫酸、二乙基羟胺、羟胺硫酸盐、偏亚硫酸氢钠/铵/钾和亚硫酸钠/铵/钾和选自N-烷基-N-苄基-N,N-二甲基氯化铵和4-(3-苯基丙基)吡啶的季铵盐表面活性剂。
14.根据权利要求1所述的组合物,其进一步包含络合剂。
15.根据权利要求14所述的组合物,其中所述络合剂选自酞酸、琥珀酸、柠檬酸、酒石酸、苹果酸、葡萄糖酸、天冬氨酸、阿拉伯糖醇、赤藓糖醇、甘油、氢化淀粉水解物、异麦芽糖醇、乳糖醇、麦芽糖醇、甘露醇、山梨醇、木糖醇、乙酸、丙酮肟、丙烯酸、己二酸、丙氨酸、精氨酸、天冬酰胺、天冬氨酸、甜菜碱、二甲基乙二肟、甲酸、富马酸、葡糖酸、谷氨酸、谷胺酰胺、戊二酸、甘油酸、甘油、乙醇酸、乙醛酸、组氨酸、亚氨基二乙酸、异酞酸、衣康酸、乳酸、亮氨酸、赖氨酸、马来酸、马来酸酐、苹果酸、丙二酸、扁桃酸、2,4-戊二酮、苯基乙酸、苯丙氨酸、酞酸、脯氨酸、丙酸、邻苯二酚、均苯四甲酸、奎尼酸、丝氨酸、山梨醇、琥珀酸、酒石酸、对苯二甲酸、偏苯三甲酸、对称苯三甲酸、酪氨酸、缬氨酸、木糖醇、乙二胺、草酸、单宁酸、吡啶甲酸、1,3-环戊烷二酮、儿茶酚、焦棓酚、间苯二酚、氢醌、氰尿酸、巴比妥酸、1,2-二甲基巴比妥酸、丙酮酸、丙硫醇、苯甲羟肟酸、四亚乙基五胺、4-(2-羟乙基)吗啉、N-氨基乙基哌嗪、乙二胺四乙酸、1,2-环己二胺-N,N,N',N'-四乙酸、N-(羟乙基)-乙二胺三乙酸、亚氨基二乙酸、2-(羟乙基)亚氨基二乙酸、次氮基三乙酸、氨基三(亚甲基膦酸)、羟基次乙基二膦酸、乙二氨基四(亚甲基膦酸)、乙二氨基五(亚甲基膦酸)、硫脲、1,1,3,3-四甲基脲、脲、脲衍生物、甘氨酸、半胱氨酸、谷氨酸、异亮氨酸、甲硫氨酸、哌啶、N-(2-氨基乙基)哌啶、吡咯烷、苏氨酸、色氨酸、水杨酸、二吡啶甲酸、对甲苯磺酸、5-磺基水杨酸、丙烷-1,2,3-三甲酸、丁烷-1,2,3,4-四甲酸、戊烷-1,2,3,4,5-五甲酸、偏苯三甲酸、均苯三甲酸、均苯四甲酸、苯六甲酸;含羧酸基团低聚物和聚合物,其衍生自包括丙烯酸、甲基丙烯酸、马来酸、琥珀酸、天冬氨酸、2-丙烯酰胺基-2-甲基-1-丙磺酸、丙烯酰胺、膦酸甲基丙烯酰胺基丙基三甲基氯化铵、烯丙基卤化物中的一或多者的单体;及其组合。
16.根据权利要求1所述的组合物,其进一步包含水溶性或水可分散性聚合物。
17.根据权利要求16所述的组合物,其中所述水溶性或水可分散性聚合物选自甲基丙烯酸均聚物和与丙烯酰胺基甲基丙磺酸和马来酸的共聚物;马来酸/乙烯基醚共聚物;聚(乙烯基吡咯烷酮)/乙酸乙烯酯;膦酸化聚乙二醇低聚物、聚(丙烯酸)、聚(丙烯酰胺)、聚(乙酸乙烯酯)、聚(乙二醇)、聚丙二醇、聚(苯乙烯磺酸)、聚(乙烯基磺酸)、聚(乙烯基膦酸)、聚(乙烯基磷酸)、聚(乙烯亚胺)、聚(丙烯亚胺)、聚烯丙胺、聚环氧乙烷、聚乙烯基吡咯烷酮、PPG-PEG-PPG嵌段共聚物、PEG-PPG-PEG嵌段共聚物、聚(乙烯醇)、聚丙烯酸(羟乙基)酯、聚甲基丙烯酸(羟乙基)酯、羟乙基纤维素、甲基羟乙基纤维素、羟丙基纤维素、甲基羟丙基纤维素、黄原胶、藻酸钾、果胶、羧甲基纤维素、葡糖胺、聚(二烯丙基二甲基铵)氯化物、聚(2-丙烯酰胺基-2-甲基-1-丙磺酸)、聚(苯乙烯磺酸)、聚乙烯基吡咯烷酮、PVA-聚(2-丙烯酰胺基-2-甲基-1-丙磺酸)共聚物、聚乙二醇化甲基丙烯酸酯/丙烯酸酯共聚物、聚(2-甲基丙烯酰氧基乙基三甲基氯化铵)及其共聚物、二甲氨基甲基丙烯酸酯聚合物及其共聚物、三甲基铵甲基丙烯酸甲酯聚合物及其共聚物、二甲氨基甲基丙烯酸酯聚合物及其共聚物、三甲基铵甲基丙烯酸甲酯聚合物及其共聚物、及其组合。
18.根据权利要求1所述的组合物,其进一步包含杀生物剂。
19.根据权利要求1所述的组合物,其进一步包含氢键结化合物。
20.一种自其上具有残留物和污染物的微电子装置移除所述残留物和污染物的方法,所述方法包括使所述微电子装置与清洁组合物接触足以自所述微电子装置至少部分清洁所述残留物和污染物的时间,其中所述清洁组合物包含:
a.水;
b.具有2到7个碳原子的烷醇胺;
c.二醇醚;
d.pH调节剂;和
e.表面活性疏水性酸。
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- 2021-10-01 WO PCT/US2021/053206 patent/WO2022076265A1/en active Application Filing
- 2021-10-01 CN CN202180076458.3A patent/CN116457447A/zh active Pending
- 2021-10-01 KR KR1020237014952A patent/KR20230079429A/ko unknown
- 2021-10-01 EP EP21878273.8A patent/EP4225882A1/en active Pending
- 2021-10-01 JP JP2023521040A patent/JP2023545035A/ja active Pending
- 2021-10-01 US US17/492,257 patent/US11905491B2/en active Active
- 2021-10-04 TW TW110136890A patent/TW202227603A/zh unknown
Also Published As
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KR20230079429A (ko) | 2023-06-07 |
EP4225882A1 (en) | 2023-08-16 |
WO2022076265A1 (en) | 2022-04-14 |
US20220106542A1 (en) | 2022-04-07 |
TW202227603A (zh) | 2022-07-16 |
JP2023545035A (ja) | 2023-10-26 |
US11905491B2 (en) | 2024-02-20 |
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