CN118085973A - 化学机械抛光后调配物及其使用方法 - Google Patents
化学机械抛光后调配物及其使用方法 Download PDFInfo
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- CN118085973A CN118085973A CN202410234576.8A CN202410234576A CN118085973A CN 118085973 A CN118085973 A CN 118085973A CN 202410234576 A CN202410234576 A CN 202410234576A CN 118085973 A CN118085973 A CN 118085973A
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- 238000000034 method Methods 0.000 title claims abstract description 32
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- 238000004377 microelectronic Methods 0.000 claims abstract description 53
- 239000000356 contaminant Substances 0.000 claims abstract description 41
- 239000000463 material Substances 0.000 claims abstract description 36
- 150000008044 alkali metal hydroxides Chemical class 0.000 claims abstract description 29
- 229910001860 alkaline earth metal hydroxide Inorganic materials 0.000 claims abstract description 29
- 239000008139 complexing agent Substances 0.000 claims description 52
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- LPSKDVINWQNWFE-UHFFFAOYSA-M tetrapropylazanium;hydroxide Chemical compound [OH-].CCC[N+](CCC)(CCC)CCC LPSKDVINWQNWFE-UHFFFAOYSA-M 0.000 claims description 4
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- 239000000811 xylitol Substances 0.000 claims description 3
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- JPIGSMKDJQPHJC-UHFFFAOYSA-N 1-(2-aminoethoxy)ethanol Chemical compound CC(O)OCCN JPIGSMKDJQPHJC-UHFFFAOYSA-N 0.000 claims description 2
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Classifications
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- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- 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
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- 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
- H01L21/02063—Cleaning during device manufacture during, before or after processing of insulating layers the processing being the formation of vias or contact holes
-
- 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
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- C11D3/0073—Anticorrosion compositions
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- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
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-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
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-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
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- C11D3/16—Organic compounds
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- 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
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- 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
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- C11D7/265—Carboxylic acids or salts thereof
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
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-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
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- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
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- 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
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- C11D7/3227—Ethers 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
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- C11D7/3245—Aminoacids
-
- 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
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-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D7/00—Compositions of detergents based essentially on non-surface-active compounds
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- C11D7/34—Organic compounds containing sulfur
-
- 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
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-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
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- H01L21/02052—Wet cleaning only
-
- H—ELECTRICITY
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- H—ELECTRICITY
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- H01L21/02068—Cleaning during device manufacture during, before or after processing of conductive layers, e.g. polysilicon or amorphous silicon layers
- H01L21/02074—Cleaning during device manufacture during, before or after processing of conductive layers, e.g. polysilicon or amorphous silicon layers the processing being a planarization of conductive layers
-
- C—CHEMISTRY; METALLURGY
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Abstract
本申请涉及一种化学机械抛光后调配物及其使用方法。本发明揭示一种用于从上面具有化学机械抛光CMP后残余物及污染物的微电子装置清除所述残余物及污染物的清洁组合物及方法。所述清洁组合物基本上没有碱金属氢氧化物、碱土金属氢氧化物及四甲基氢氧化铵。所述组合物实现了在不危害低k电介质材料或铜互连材料的情况下从所述微电子装置的表面高效地清除所述CMP后残余物及污染物材料。
Description
本申请是申请日为2016年01月05日、申请号为201680008165.0、发明名称为“化学机械抛光后调配物及其使用方法”的发明专利申请的分案申请。
技术领域
本发明一般来说涉及用于从上面具有残余物及/或污染物的微电子装置清除所述残余物及/或污染物的没有四甲基氢氧化铵的组合物,其中所述组合物已改善钴的兼容性。
背景技术
微电子装置晶片用于形成集成电路。微电子装置晶片包含衬底,例如硅,所述衬底区域被图案化以用于沉积具有绝缘、导电或半导电性质的不同材料。
为获得正确图案化,必须移除在于衬底上形成若干层中所使用的过量材料。此外,为制作功能性且可靠电路,在后续处理之前制备扁平或平坦的微电子晶片表面是重要的。因此,有必要移除及/或抛光微电子装置晶片的特定表面。
化学机械抛光或平坦化(“CMP”)是其中从微电子装置晶片的表面移除材料并通过耦合物理工艺(例如磨蚀)与化学工艺(例如氧化反应或螯合作用)而抛光表面(更明确地说,将表面平坦化)的工艺。在其最基本形式中,CMP涉及将浆料(例如,研磨剂与活性化学物质的溶液)施加到抛光垫,所述抛光垫擦拭微电子装置晶片的表面以实现移除、平坦化及抛光工艺。不期望移除或抛光工艺由纯物理或纯化学动作构成,而是两者进行协同组合来实现快速均匀移除。在集成电路的制作中,CMP浆料还应能够优先地移除包括金属与其它材料的复杂层的膜,使得可为后续光学光刻或图案化、蚀刻及薄膜处理产生高度平坦的表面。
近期,铜越来越多地被用于集成电路中的金属互连件。在微电子装置制作中通常用于电路的金属化的铜镶嵌工艺中,必须被移除及平坦化的层包含具有约1μm-1.5μm的厚度的铜层及具有约0.05μm-0.15μm的厚度的铜晶种层。这些铜层通过通常为约 厚的阻挡材料层而与电介质材料表面分离,此防止铜扩散到氧化物电介质材料中。在抛光之后跨越晶片表面获得良好均匀性的一个关键是使用针对每一材料具有正确移除选择性的CMP浆料。
涉及晶片衬底表面制备、沉积、镀敷、蚀刻及化学机械抛光的前述处理操作需要各种清洁操作以确保微电子装置产品不具有否则将不利地影响产品的功能或甚至致使产品无法用于其预期功能的污染物。通常,这些污染物的粒子小于0.3μm。
关于此的一个特定问题是在CMP处理之后留在微电子装置衬底上的残余物。此类残余物包含CMP材料及腐蚀抑制剂化合物,例如苯并三唑(BTA)。如果不移除,那么这些残余物可导致对铜线的损坏或使铜金属化严重不平,并且导致CMP后所施加的层在装置衬底上具有不良粘合性。铜金属化的严重不平是尤其成问题的,因为过度粗糙的铜可导致产品微电子装置的不良电性能。
对于微电子装置制造常见的另一残余物产生工艺涉及用以将经显影光致抗蚀剂涂层的图案转印到下伏层的气相等离子蚀刻,所述下伏层可由硬掩模、层间电介质(ILD)及蚀刻停止层组成。气相等离子蚀刻后残余物通常沉积在后段工艺(BEOL)结构上,且如果不进行移除,那么可妨碍后续硅化或触点形成,所述气相等离子蚀刻后残余物可包含衬底上及等离子气体中存在的化学元素。常规清洁化学物质通常会损坏ILD、被吸收到ILD的孔隙中,借此增加介电常数及/或腐蚀金属结构。
此项技术内持续需要提供有效地从衬底移除残余物(例如,CMP后残余物、蚀刻后残余物及灰化后残余物)的组合物及方法。所述组合物比现有技术组合物更环保且可包含创新组分,且因此可被视为现有技术的组合物的替代物。
发明内容
本发明一般来说涉及一种用于从上面具有残余物及污染物的微电子装置清除所述残余物及/或污染物的组合物及工艺。本发明的清洁组合物基本上没有碱金属氢氧化物、碱土金属氢氧化物及四甲基氢氧化铵。所述残余物可包含CMP后残余物、蚀刻后残余物及/或灰化后残余物。有利地,本文中所描述的组合物相对于现有技术中的组合物展示经改善钴兼容性。
在一个方面中,描述一种组合物,所述组合物包括至少一种有机胺、至少一种溶剂、至少一种季碱、至少一种络合剂、任选地至少一种还原剂、任选地至少一种额外蚀刻剂及任选地至少一种清洁添加剂,其中清洁组合物基本上没有碱金属氢氧化物、碱土金属氢氧化物及四甲基氢氧化铵。
在另一方面中,描述一种组合物,所述组合物包括至少一种有机胺、至少一种溶剂、至少一种季碱、至少一种络合剂、至少一种还原剂、任选地至少一种额外蚀刻剂及任选地至少一种清洁添加剂,其中清洁组合物基本上没有碱金属氢氧化物、碱土金属氢氧化物及四甲基氢氧化铵。
在又一方面中,描述一种组合物,所述组合物包括至少一种有机胺、至少一种溶剂、至少一种季碱、至少一种络合剂、至少一种额外蚀刻剂、任选地至少一种还原剂及任选地至少一种清洁添加剂,其中清洁组合物基本上没有碱金属氢氧化物、碱土金属氢氧化物及四甲基氢氧化铵。
在又一方面中,描述一种从上面具有残余物及污染物的微电子装置移除所述残余物及污染物的方法,所述方法包括使所述微电子装置与清洁组合物接触达足以从所述微电子装置至少部分地清除所述残余物及污染物的时间,其中所述清洁组合物包括至少一种有机胺、至少一种溶剂、至少一种季碱、至少一种络合剂、任选地至少一种还原剂、任选地至少一种额外蚀刻剂及任选地至少一种清洁添加剂,其中所述清洁组合物基本上没有碱金属氢氧化物、碱土金属氢氧化物及四甲基氢氧化铵。
依据以下揭示内容及所附权利要求书将更全面地明了其它方面、特征及优点。
具体实施方式
本发明一般来说涉及用于从上面具有残余物及污染物的微电子装置移除此些材料的组合物。所述组合物对于移除CMP后残余物、蚀刻后残余物或灰化后残余物是特别有用的。
为便于参考,“微电子装置”对应于半导体衬底、平板显示器、相变存储器装置、太阳能面板及经制造供在微电子器件、集成电路或计算机芯片应用中使用的其它产品,所述产品包含太阳能衬底、光伏及微机电系统(MEMS)。太阳能衬底包含但不限于硅、非晶硅、多晶硅、单晶硅、CdTe、铜铟硒化物、铜铟硫化物及镓上砷化镓。太阳能衬底可经掺杂或未经掺杂。应理解,术语“微电子装置”并非意欲以任何方式为限制性的且包含最终将成为微电子装置或微电子组合件的任何衬底。
如本文中所使用,“残余物”对应于在微电子装置的制造(包含但不限于等离子蚀刻、灰化、化学机械抛光、湿法蚀刻及其组合)期间产生的粒子。
如本文中所使用,“污染物”对应于CMP浆料中存在的化学物质、抛光浆料的反应副产物、湿法蚀刻组合物中存在的化学物质、湿法蚀刻组合物的反应副产物,及为CMP工艺、湿法蚀刻工艺、等离子蚀刻工艺或等离子灰化工艺的副产物的任何其它材料。
如本文中所使用,“CMP后残余物”对应于来自抛光浆料的粒子(例如,含二氧化硅的粒子)、浆料中存在的化学物质、抛光浆料的反应副产物、富含碳的粒子、抛光垫粒子、刷下料(brush deloading)粒子、装备的构造材料粒子、金属、金属氧化物、有机残余物,及为CMP工艺的副产物的任何其它材料。如本文中所定义,通常被抛光的“金属”包含铜、铝及钨。
如本文中所定义,“低k电介质材料”对应于用作分层微电子装置中的电介质材料的任何材料,其中材料具有小于约3.5的介电常数。优选地,低k电介质材料包含低极性材料,例如含硅有机聚合物、含硅混合有机/无机材料、有机硅酸盐玻璃(OSG)、TEOS、氟化硅酸盐玻璃(FSG)、二氧化硅及碳掺杂氧化硅(CDO)玻璃。应了解,低k电介质材料可具有变化的密度及变化的多孔性。
如本文中所定义,“络合剂”包含所属领域的技术人员理解为络合剂、螯合剂及/或掩蔽剂的那些化合物。络合剂将以化学方式与使用本文中所描述的组合物将移除的金属原子及/或金属离子组合或以物理方式保持所述金属原子及/或金属离子。
如本文中所定义,术语“阻挡材料”对应于此项技术内用于密封金属线(例如,铜互连件)以使所述金属(例如,铜)到电介质材料中的扩散最小化的任何材料。优选阻挡层材料包含钽、钛、钌、铪、钨、钴及其它难熔金属以及其氮化物及硅化物。
如本文中所定义,“蚀刻后残余物”对应于气相等离子蚀刻工艺(例如,BEOL双镶嵌处理或湿法蚀刻工艺)之后剩余的材料。蚀刻后残余物本质上可是有机的、有机金属的、有机硅的或无机的,举例来说,含硅材料、基于碳的有机材料及蚀刻气体残余物,例如氧气及氟气。
如本文中所定义,如本文中所使用的“灰化后残余物”对应于氧化性或还原性等离子灰化以移除变硬的光致抗蚀剂及/或底部抗反射涂层(BARC)材料之后剩余的材料。灰化后残余物本质上可是有机的、有机金属的、有机硅的或无机的。
“基本上没有”在本文中定义为小于2wt.%、优选地小于1wt.%、更优选地小于0.5wt.%且最优选地小于0.1wt.%。在一个实施例中,“基本上没有”对应于零百分比。
如本文中所定义,含钴材料包含基于材料的总重量包括大于50wt%的元素钴的任何材料。含钴材料的实例包含但不限于纯钴、氮化钴(包含包括例如Ta或Li的额外元素的氮化钴)、CoP、CoSi及硅化钴。
如本文中所使用,“约”用于对应于标注值的±5%。
如本文中所定义,“反应或降解产物”包含但不限于:作为表面处的催化作用、氧化反应、还原反应、与组成组分的反应或以其它方式进行聚合的结果而形成的产品或副产物;作为改变或转变的结果而形成的产品或副产物,在所述改变或转变中,物质或材料(例如,分子、化合物等)与其它物质或材料进行组合、与其它物质或材料交换成分、进行分解、进行重排或以其它方式以化学方式及/或以物理方式被更改,所述产品或副产物包含前述反应、改变及/或转变中的任一者或者前述反应、改变及/或转变的任何组合的中间产物或副产物。应了解,反应或降解产物可具有比原始反应物大或小的摩尔质量。
如本文中所使用,用于从上面具有残余物及污染物的微电子装置清除所述残余物及污染物的“适合性”对应于从微电子装置至少部分地移除所述残余物/污染物。清洁效力由微电子装置上的目标的还原反应估定。举例来说,清洁前及清洁后分析可使用原子力显微镜而实施。样本上的粒子可显现为像素的范围。直方图(例如,Sigma Scan Pro)可应用于滤波某一强度(例如,231-235)中的像素且对粒子的数目进行计数。粒子还原可使用以下式子而计算;
注意,确定清洁效力的方法仅以举例方式提供且不打算限于此。另一选择为,清洁效力可视为由颗粒物覆盖的总表面的百分比。举例来说,AFM可经编程以执行z平面扫描以识别高于某一高度阈值的所关注形貌区且接着计算由所述所关注区覆盖的总表面的面积。所属领域的技术人员将易于理解,在清洁后由所述所关注区覆盖的面积越小,清洁组合物的效用越大。优选地,使用本文中所描述的组合物从微电子装置移除残余物/污染物的至少75%,移除残余物/污染物的更优选地至少90%、甚至更优选地至少95%及最优选地至少99%。
本文中所描述的组合物可体现于各种各样的特定调配物中,如下文中更全面地描述。
在所有此些组合物中,其中参考重量百分比范围(包含零下限)论述组合物的特定组分,将理解,此些组分可存在于或不存在于组合物的各种具体实施例中,且在其中存在此些组分的例子中,所述组分可基于其中采用此些组分的组合物的总重量以低至0.001重量百分比的浓度存在。
在第一方面中,清洁组合物包括以下各项、由以下各项组成或基本上由以下各项组成:至少一种有机胺、至少一种溶剂(例如,水)、至少一种季碱、任选地至少一种络合剂、任选地至少一种还原剂、任选地至少一种额外蚀刻剂及任选地至少一种清洁添加剂,其中所述清洁组合物基本上没有碱金属氢氧化物、碱土金属氢氧化物及四甲基氢氧化铵。在一个实施例中,所述清洁组合物包括以下各项、由以下各项组成或基本上由以下各项组成:至少一种有机胺、至少一种溶剂(例如,水)、至少一种络合剂及至少一种季碱,其中所述清洁组合物基本上没有碱金属氢氧化物、碱土金属氢氧化物及四甲基氢氧化铵。在另一实施例中,所述清洁组合物包括以下各项、由以下各项组成或基本上由以下各项组成:至少一种有机胺、至少一种溶剂(例如,水)、至少一种季碱及至少一种还原剂,其中所述清洁组合物基本上没有碱金属氢氧化物、碱土金属氢氧化物及四甲基氢氧化铵。在另一实施例中,所述清洁组合物包括以下各项、由以下各项组成或基本上由以下各项组成:至少一种有机胺、至少一种溶剂(例如,水)、至少一种还原剂、至少一种络合剂及至少一种季碱,其中所述清洁组合物基本上没有碱金属氢氧化物、碱土金属氢氧化物及四甲基氢氧化铵。在又一实施例中,所述清洁组合物包括以下各项、由以下各项组成或基本上由以下各项组成:至少一种有机胺、至少一种溶剂(例如,水)、至少一种络合剂、至少一种季碱及至少一种额外蚀刻剂,其中所述清洁组合物基本上没有碱金属氢氧化物、碱土金属氢氧化物及四甲基氢氧化铵。在又一实施例中,所述清洁组合物包括以下各项、由以下各项组成或基本上由以下各项组成:至少一种有机胺、至少一种溶剂(例如,水)、至少一种络合剂、至少一种季碱及至少一种清洁添加剂,其中所述清洁组合物基本上没有碱金属氢氧化物、碱土金属氢氧化物及四甲基氢氧化铵。在另一实施例中,所述清洁组合物包括以下各项、由以下各项组成或基本上由以下各项组成:至少一种有机胺、至少一种溶剂(例如,水)、至少一种还原剂、至少一种络合剂、至少一种季碱及至少一种额外蚀刻剂,其中所述清洁组合物基本上没有碱金属氢氧化物、碱土金属氢氧化物及四甲基氢氧化铵。在又一实施例中,所述清洁组合物包括以下各项、由以下各项组成或基本上由以下各项组成:至少一种有机胺、至少一种溶剂(例如,水)、至少一种还原剂、至少一种络合剂、至少一种季碱及至少一种额外清洁添加剂,其中所述清洁组合物基本上没有碱金属氢氧化物、碱土金属氢氧化物及四甲基氢氧化铵。在又一实施例中,所述清洁组合物包括以下各项、由以下各项组成或基本上由以下各项组成:至少一种有机胺、至少一种溶剂(例如,水)、至少一种还原剂、至少一种络合剂、至少一种季碱、至少一种额外蚀刻剂及至少一种额外清洁添加剂,其中所述清洁组合物基本上没有碱金属氢氧化物、碱土金属氢氧化物及四甲基氢氧化铵。有利地,本文中所描述的组合物相对于现有技术中的组合物展示经改善钴兼容性。
在一个优选实施例中,第一方面的清洁组合物包括以下各项、由以下各项组成或基本上由以下各项组成:至少一种季碱、至少一种有机胺、至少一种络合剂、至少一种溶剂(例如,水)及至少一种还原剂,其中至少一种络合剂包括半胱氨酸,其中所述清洁组合物基本上没有碱金属氢氧化物、碱土金属氢氧化物及四甲基氢氧化铵,其中所述清洁组合物按以下经浓缩实施例进行调配,其中所有百分比均是基于调配物的总重量按重量计算得出:
当存在时,半胱氨酸的量优选地介于从约0.00005wt%到约0.2wt%的范围内。尽管不希望受理论束缚,但当半胱氨酸的量大于约0.2wt%时,铜及钴上会形成极厚钝化层,所述极厚钝化层无法被轻易地冲洗掉且因此促成有机残余物。重量百分率如下:有机胺/络合剂介于从约1到约200、优选地约10到约150、更优选地约50到约120的范围内;季碱/络合剂介于从约1到约300、优选地约10到约250、更优选地约50到约200或者优选地约1到约10的范围内;及还原剂/络合剂介于从约1到约200、优选地约10到约150、更优选地约50到约120的范围内。
在另一优选实施例中,第一方面的清洁组合物包括以下各项、由以下各项组成或基本上由以下各项组成:至少一种有机胺、至少一种络合剂、至少一种溶剂(例如,水)及至少一种季碱,其中至少一种络合剂包括半胱氨酸,其中所述清洁组合物基本上没有碱金属氢氧化物、碱土金属氢氧化物及四甲基氢氧化铵,其中所述清洁组合物按以下经浓缩实施例进行调配,其中所有百分比均是基于调配物的总重量按重量计算得出:
当存在时,半胱氨酸的量优选地介于从约0.00005wt%到约0.2wt%的范围内。重量百分率如下:有机胺/络合剂介于从约1到约200、优选地约10到约150、更优选地约50到约120的范围内;及季碱/络合剂介于从约1到约300、优选地约10到约250、更优选地约50到约200或者优选地约1到约10的范围内。
在又一实施例中,所述清洁组合物包括以下各项、由以下各项组成或基本上由以下各项组成:至少一种有机胺、半胱氨酸、至少一种额外络合剂、至少一种季碱、水、任选地至少一种额外蚀刻剂及任选地至少一种清洁添加剂,其中所述清洁组合物按以下经浓缩实施例进行调配,其中所有百分比均是基于调配物的总重量按重量计算得出:
重量百分率如下:有机胺/半胱氨酸介于从约1到约200、优选地约10到约150、更优选地约50到约120的范围内;季碱/半胱氨酸介于从约0.1到约100、优选地约1到约60、更优选地约2到约25的范围内;及络合剂/半胱氨酸介于从约0.01到约50、优选地约0.1到约30、更优选地约1到约10的范围内。
在又一优选实施例中,第一方面的清洁组合物包括以下各项、由以下各项组成或基本上由以下各项组成:至少一种有机胺、至少一种络合剂、至少一种溶剂(例如,水)、至少一种季碱及至少一种额外蚀刻剂,其中至少一种络合剂包括半胱氨酸,其中所述清洁组合物基本上没有碱金属氢氧化物、碱土金属氢氧化物及四甲基氢氧化铵,且其中半胱氨酸的量基于组合物的总重量介于从约0.00005wt%到约0.2wt%的范围内。重量百分率如下:有机胺/络合剂介于从约1到约200、优选地约1到约40、更优选地约1到约20的范围内;季碱/络合剂介于从约1到约300、优选地约10到约100、更优选地约20到约80或者约1到约10的范围内;及额外蚀刻剂/络合剂介于从约1到约100、优选地约10到约80、更优选地约10到约50的范围内。
可用于特定组合物中的说明性有机胺包含具有通式NR1R2R3的物质,其中R1、R2及R3可彼此相同或不同,且选自由以下各项组成的群组:氢、直链或支链C1-C6烷基(例如,甲基、乙基、丙基、丁基、戊基及己基)、直链或支链C1-C6醇(例如,甲醇、乙醇、丙醇、丁醇、戊醇、及己醇)以及具有化学式R4-O-R5的直链或支链醚,其中R4及R5可彼此相同或不同,且选自由如上文所定义的C1-C6烷基组成的群组。最优选地,R1、R2及R3中的至少一者是直链或支链C1-C6醇。实例包含但不限于烷醇胺,例如氨基乙基乙醇胺、N-甲氨基乙醇、氨基乙氧基乙醇、二甲基氨基乙氧基乙醇、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、异丙胺、2-氨基-1-丁醇、异丁醇胺、其它C1-C8烷醇胺及其组合;胺,例如三乙烯二胺、乙二胺、己二胺、二乙烯三胺、三乙基胺、三甲基胺及其组合;二甘醇胺;吗啉;及胺与烷醇胺的组合。当胺包含醚组分时,胺可被视为烷氧基胺,例如,1一甲氧基-2一氨基乙烷。优选地,有机胺包括单乙醇胺。
当存在时,还原剂包含但不限于抗坏血酸、L(+)-抗坏血酸、异抗坏血酸、抗坏血酸衍生物、没食子酸、甲脒亚磺酸、尿酸、酒石酸、半胱氨酸及其任何组合。优选地,还原剂包括抗坏血酸、酒石酸或其组合。
季碱包含具有化学式NR1R2R3R4OH的化合物,其中R1、R2、R3及R4可彼此相同或不同,且选自由以下各项组成的群组:氢、直链或支链C2-C6烷基(例如,甲基、乙基、丙基、丁基、戊基及己基)及经取代或未经取代C6-C10芳基,例如,苄基。商业上可获得的四烷基氢氧化铵包含四乙基氢氧化铵(TEAH)、四丙基氢氧化铵(TPAH)、四丁基氢氧化铵(TBAH)、三丁基甲基氢氧化铵(TBMAH)、苄基三甲基氢氧化铵(BTMAH)、胆碱氢氧化物、乙基三甲基氢氧化铵、三(2-羟基乙基)甲基氢氧化铵、二乙基二甲基氢氧化铵及其组合。商业上不可获得的四烷基氢氧化铵可以类似于用于制备TEAH、TPAH、TBAH、TBMAH及BTMAH的已公布合成方法的方式来制备,所述合成方法为所属领域的技术人员已知的。另一选择为或另外,至少一种季碱可係具有化学式(PR1R2R3R4)OH的化合物,其中R1、R2、R3及R4可彼此相同或不同,且选自由以下各项组成的群组:氢、直链C1-C6烷基(例如,甲基、乙基、丙基、丁基、戊基、己基)、支链C1-C6烷基、C1-C6烷醇(例如,甲醇、乙醇、丙醇、丁醇、戊醇、己醇)、经取代C6-C10芳基、未经取代C6-C10芳基(例如,苄基)及其任何组合,例如四丁基氢氧化鏻(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。优选地,季碱包括胆碱氢氧化物。
本文中所涵盖的络合剂包含但不限于乙酸、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、反丁烯二酸、葡糖酸、谷氨酸、谷氨酰胺、戊二酸、甘油酸、甘油、乙醇酸、乙醛酸、组氨酸、亚氨基二乙酸、间苯二甲酸、衣康酸、乳酸、亮氨酸、赖氨酸、顺丁烯二酸、顺丁烯二酸酐、苹果酸、丙二酸、扁桃酸、2,4-乙酰基丙酮、苯基乙酸、苯基丙氨酸、邻苯二甲酸、脯氨酸、丙酸、焦儿茶酚、苯均四酸、奎尼酸、丝氨酸、山梨醇、琥珀酸、酒石酸、对苯二甲酸、偏苯三酸、苯均三酸、酪氨酸、缬氨酸、木糖醇、乙二胺、草酸、丹宁酸、苯甲酸、苯甲酸铵、邻苯二酚、连苯三酚、间苯二酚、对苯二酚、氰尿酸、巴比土酸及衍生物(例如1,2-二甲基巴比土酸)、α-酮酸(例如丙酮酸)、丙硫醇、苯基异羟肟酸、四乙基五胺(TEPA)、4-(2-羟基乙基)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)、甘氨酸/抗坏血酸、亚氨基二乙酸(IDA)、2-(羟基乙基)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、丙氨酸、精氨酸、天冬酰胺、天冬氨酸、半胱氨酸、谷氨酸、戊二酸、谷氨酰胺、组氨酸、异亮氨酸、亮氨酸、赖氨酸、蛋氨酸、苯基丙氨酸、哌啶、N-(2-氨基乙基)哌啶、脯氨酸、吡咯烷、丝氨酸、苏氨酸、色氨酸、酪氨酸、缬氨酸、膦酸及其衍生物(例如l-羟基亚乙基-l,1-二膦酸(HEDP))、l,5,9-三氮杂环十二烷-N,N′,N″-三(亚甲基膦酸)(DOTRP)、l,4,7,10-四氮杂环十二烷-N,N′,N″,N″′-四(亚甲基膦酸)(DOTP)、次氮基三(亚甲基)三膦酸、二乙烯三胺五(亚甲基膦酸)(DETAP)、氨基三(亚甲基膦酸)、双(六亚甲基)三胺膦酸、l,4,7-三氮杂环壬烷-N,N′,N″-三(亚甲基膦酸)(NOTP)、盐及其衍生物,以及其组合。在优选实施例中,优选地,络合剂包括半胱氨酸、草酸、二甲基乙二肟、酒石酸或其任何组合。在一个优选实施例中,络合剂包括半胱氨酸及草酸。
当存在时,至少一种额外蚀刻剂包含但不限于吗啉、二甘醇胺、3-丁氧基丙胺、丙二醇单丁醚(例如,DOWANOL PnB(陶氏化学公司))、羟基乙基吗啉、羟基丙基吗啉、氨基乙基吗啉、氨基丙基吗啉、五甲基二乙烯三胺(PMDETA)、三甲基氨基乙基乙醇胺、三甲基氨基丙基乙醇胺及其组合。当存在时,至少一种额外蚀刻剂包括吗啉、二甘醇胺或其组合。
当存在时,所述至少一种清洁添加剂包含但不限于:羟基丙基纤维素、羟基乙基纤维素、羧基甲基纤维素、钠羧基甲基纤维素(Na CMC)、聚乙烯吡咯烷酮(PVP)、使用N-乙烯基吡咯烷酮单体制成的任何聚合物、聚丙烯酸酯及聚丙烯酸酯的类似物、聚氨基酸(例如,聚丙氨酸、聚亮氨酸、聚甘氨酸等)、聚酰胺基羟基尿烷、聚内酯、聚丙烯酰胺、黄原胶、壳聚糖、聚环氧乙烷、聚乙烯醇、聚乙酸乙烯酯、聚丙烯酸、聚乙烯亚胺、糖醇(例如山梨醇及木糖醇)、脱水山梨醇的酯、仲醇乙氧基化物(例如TERGITOL)及其组合。当存在时,所述至少一种清洁添加剂基于组合物的总重量以从约0.0001wt%到约1wt%、优选地从约0.0001wt%到约0.2wt%的量存在于第一方面的清洁组合物中。
在特别优选实施例中,第一方面的清洁组合物包括以下各项、由以下各项组成或基本上由以下各项组成:胆碱氢氧化物、至少一种胺、至少一种络合剂、至少一种还原剂及水,其中所述清洁组合物基本上没有碱金属氢氧化物、碱土金属氢氧化物及四甲基氢氧化铵。举例来说,第一方面的清洁组合物可包括以下各项、由以下各项组成或基本上由以下各项组成:胆碱氢氧化物、至少一种烷醇胺、半胱氨酸、至少一种还原剂及水,优选地胆碱氢氧化物、单乙醇胺(MEA)、半胱氨酸、抗坏血酸及水,其中所述清洁组合物基本上没有碱金属氢氧化物、碱土金属氢氧化物及四甲基氢氧化铵,且其中半胱氨酸的量介于从约0.00005wt%到约0.2wt%的范围内。重量百分率如下:有机胺/络合剂介于从约1到约200、优选地约10到约1 50、更优选地约50到约120的范围内;胆碱氢氧化物/络合剂介于从约1到约300、优选地约10到约250、更优选地约50到约200或者优选地约1到约1 0的范围内;及还原剂/络合剂介于从约1到约200、优选地约10到约150、更优选地约50到约120的范围内。
在另一特别优选实施例中,第一方面的清洁组合物包括以下各项、由以下各项组成或基本上由以下各项组成:至少一种胺、半胱氨酸、胆碱氢氧化物及水,其中所述清洁组合物基本上没有碱金属氢氧化物、碱土金属氢氧化物及四甲基氢氧化铵。举例来说,所述清洁组合物可包括以下各项、由以下各项组成或基本上由以下各项组成:至少一种烷醇胺、半胱氨酸、胆碱氢氧化物及水,优选地单乙醇胺、半胱氨酸、胆碱氢氧化物、任选地酒石酸及水,其中所述清洁组合物基本上没有碱金属氢氧化物、碱土金属氢氧化物及四甲基氢氧化铵,且其中半胱氨酸的量介于从约0.00005wt%到约0.2wt%的范围内。在另一实施例中,第一方面的清洁组合物可包括以下各项、由以下各项组成或基本上由以下各项组成:至少一种烷醇胺、半胱氨酸、至少一种额外络合剂、胆碱氢氧化物及水,优选地单乙醇胺、半胱氨酸、胆碱氢氧化物、草酸及水,其中所述清洁组合物基本上没有碱金属氢氧化物、碱土金属氢氧化物及四甲基氢氧化铵,且其中半胱氨酸的量介于从约0.00005wt%到约0.2wt%的范围内。重量百分率如下:有机胺/络合剂介于从约1到约200、优选地约10到约1 50、更优选地约50到约120的范围内;及季碱/络合剂介于从约1到约300、优选地约10到约250、更优选地约50到约200或者优选地约1到约10的范围内。
在又一特别优选实施例中,第一方面的清洁组合物包括以下各项、由以下各项组成或基本上由以下各项组成:至少一种胺、至少一种络合剂、胆碱氢氧化物、至少一种额外蚀刻剂及水,其中所述清洁组合物基本上没有碱金属氢氧化物、碱土金属氢氧化物及四甲基氢氧化铵。举例来说,所述清洁组合物可包括以下各项、由以下各项组成或基本上由以下各项组成:至少一种烷醇胺、半胱氨酸、胆碱氢氧化物、至少一种额外蚀刻剂、水及任选地至少一种额外络合剂,优选地(i)单乙醇胺、半胱氨酸、胆碱氢氧化物、吗啉或二甘醇胺及水,或者(ii)优选地单乙醇胺、半胱氨酸、草酸、胆碱氢氧化物、吗啉或二甘醇胺及水,其中所述清洁组合物基本上没有碱金属氢氧化物、碱土金属氢氧化物及四甲基氢氧化铵,且其中半胱氨酸的量介于从约0.00005wt%到约0.2wt%的范围内。重量百分率如下:有机胺/半胱氨酸介于从约1到约100、优选地约1到约40、更优选地约1到约20的范围内;季碱/络合剂介于从约1到约300、优选地约10到约100、更优选地约20到约80或者约1到约10的范围内;及额外蚀刻剂/络合剂介于从约1到约100、优选地约10到约80、更优选地约1 0到约50的范围内。
第一方面的清洁组合物可进一步包括至少一种金属腐蚀抑制剂。当存在时,所述至少一种金属腐蚀抑制剂被添加到第一方面的清洁组合物以降低金属(例如,铜、铝)的腐蚀速率并且增强清洁性能。所涵盖的腐蚀抑制剂包含但不限于:腺苷、腺嘌呤、吡唑、1,2,4-三唑、1,2,3-三唑、咪唑、1H-吡唑-4-羧酸、3-氨基-5-叔丁基-1H-吡唑、5-氨基-1H-四唑、4-甲基吡唑、2-巯基苯并咪唑、2-氨基-5-(乙硫基)-1,3,4-噻二唑、2-氨基-5-乙基-1,3,4-噻二唑、其衍生物,及其组合。至少一种腐蚀抑制剂的量优选地介于从约0.001wt%到约1wt%的范围内。
第一方面的清洁组合物对于从微电子装置结构清除残余物及污染物(例如,CMP后残余物、蚀刻后残余物、灰化后残余物及污染物)是特别有用的,同时还与表面上存在的含钴材料兼容。不管实施例如何,清洁组合物在从微电子装置移除残余物材料之前优选地基本上没有或没有以下各项中的至少一者:氧化剂(例如,过氧化氢);含氟源;研磨剂材料;碱金属及/或碱土金属碱;四甲基氢氧化铵;半胱氨酸的衍生物;表面活性剂;锍化合物;胺肟化合物;及其组合。另外,清洁组合物应不凝固形成聚合固体,举例来说,光致抗蚀剂。
第一方面的清洁组合物的pH大于7、优选地介于从约10到大于14的范围内、最优选地介于从约12到约14的范围内。
组分的重量百分率范围将涵盖第一方面的组合物的所有可能经浓缩或经稀释实施例。为此,在一个实施例中,提供经浓缩清洁组合物,所述经浓缩清洁组合物可经稀释以用作清洁溶液。经浓缩清洁组合物或“浓缩液”有利地准许用户(例如,CMP工艺工程师)在使用时将浓缩液稀释到所要强度及pH。经浓缩清洁组合物的稀释度可介于从约1∶1到约2500∶1、优选地约5∶1到约200∶1及最优选地约25∶1到约100∶1的范围内,其中清洁组合物在工具处或紧接在工具之前用溶剂(例如,去离子水)进行稀释。所属领域的技术人员了解,在稀释之后,本文中所揭示的组分的重量百分率的范围应保持不变。
第一方面的组合物可适用于以下应用,包含但不限于:蚀刻后残余物移除、灰化后残余物移除、表面制备、镀敷后清洁及CMP后残余物移除。另外,预期,所述清洁组合物可用于其它金属(例如,含铜)产品的清洁及保护,所述其它金属(例如,含铜)产品包含但不限于装饰性金属、金属电线接合、印刷电路板及使用金属或金属合金的其它电子封装。
在又一优选实施例中,第一方面的清洁组合物进一步包含残余物及/或污染物。残余物及污染物可溶解于组合物中。另一选择为,残余物及污染物可悬浮于组合物中。优选地,残余物包含CMP后残余物、蚀刻后残余物、灰化后残余物、污染物或其组合。
本文中所描述的清洁组合物通过简单地添加相应成分并混合为均质状态而容易地调配。此外,组合物可易于调配为在使用时或在使用之前混合的单组份调配物或多份调配物,例如,多份调配物中的个别份调配物可在工具处混合或在工具上游的储存槽中混合。相应成分的浓度可以组合物的特定倍数大范围地变化,即,更稀释或更浓缩,且将了解,本文中所描述的组合物可多方面地且替代地包括与本文中的揭示内容一致的任何成分组合、由与本文中的揭示内容一致的任何成分组合组成或基本上由与本文中的揭示内容一致的任何成分组合组成。
因此,另一方面涉及在一或多个容器中包含适于形成本文中所描述的清洁组合物的一或多种组分的试剂盒。所述试剂盒在一或多个容器中可包含用于在工厂或在使用时与溶剂(例如,水)进行组合的至少一种季碱、至少一种胺、至少一种络合剂、至少一种还原剂、水、任选地至少一种额外蚀刻剂及任选地至少一种清洁添加剂。在另一实施例中,所述试剂盒在一或多个容器中可包含用于在工厂或在使用时与溶剂(例如,水)进行组合的至少一种季碱、至少一种胺、至少一种络合剂、水、任选地至少一种额外蚀刻剂及任选地至少一种清洁添加剂。另一选择为,所述试剂盒在第一容器中可包含用于在工厂或在使用时与彼此及溶剂(例如,水)进行组合的至少一种胺、半胱氨酸、至少一种季碱及水。在另一替代方案中,所述试剂盒在一或多个容器中可包含用于在工厂或在使用时与溶剂(例如,水)进行组合的至少一种季碱、至少一种胺、半胱氨酸、至少一种额外络合剂、水、任选地至少一种额外蚀刻剂及任选地至少一种清洁添加剂。试剂盒的容器必须适于储存及运输所述清洁组合物,举例来说,容器(美国马萨诸塞州比尔里卡市的英特格公司(Entegris,Inc.))。试剂盒容器优选地基本上没有碱金属氢氧化物、碱土金属氢氧化物及四甲基氢氧化铵。
当应用于微电子制造操作时,本文中所描述的清洁组合物通常用于从微电子装置的表面清除CMP后残余物及/或污染物。清洁组合物基本上不损坏低k电介质材料、含钴材料或腐蚀装置表面上的金属互连件。优选地,清洁组合物移除在进行残余物移除之前存在于装置上的残余物的至少85%、更优选地至少90%、甚至更优选地至少95%及最优选地至少99%。
在CMP后残余物及污染物清除应用中,本文中所描述的清洁组合物可与各种各样的常规清洁工具一起使用,所述常规清洁工具例如兆声波及洗涤刷(brush scrubbing),包含但不限于Verteq单晶片兆声波Goldfinger、OnTrak系统DDS(双面洗涤器)、SEZ或其它单晶片喷射冲洗、Applied Materials Mirra-MesaTM/ReflexionTM/Reflexion LKTM及兆声波分批湿式清洗系统。
在用于从上面具有CMP后残余物、蚀刻后残余物、灰化后残余物及/或污染物的微电子装置清除所述残余物及/或污染物的组合物的使用中,清洁组合物通常在介于从约20℃到约90℃、优选地约20℃到约50℃的范围内的温度下与装置接触达从约5秒到约10分钟、优选地约1秒到20分钟、优选地约15秒到约5分钟的时间。此些接触时间及温度是说明性的,且在所述方法的广泛实践内,可采用对于从装置至少部分地清除CMP后残余物/污染物有效的任何其它适合时间及温度条件。“至少部分地清除”及“基本移除”两者均对应于移除在进行残余物移除之前存在于装置上的残余物的至少85%、更优选地至少90%、甚至更优选地至少95%且最优选地至少99%。
在实现所要清除动作之后,清洁组合物可易于从其先前已施加到的装置被移除,此在本文中所描述的组合物的给定最终用途应用中是期望的且有效的。优选地,冲洗溶液包含去离子水。此后,装置可使用氮或旋转干燥循环而干燥。
又一方面涉及根据本文中所描述的方法制成的经改善微电子装置及含有此类微电子装置的产品。
另一方面涉及循环使用的清洁组合物,其中清洁组合物可被循环使用,直到残余物及/或污染物荷载达到如所属领域的技术人员容易地确定的清洁组合物可容纳的最大量为止。
又一方面涉及使用本文中所描述的清洁组合物来制造包括微电子装置的物品的方法,所述方法包括:使微电子装置与清洁组合物接触达足以从上面具有CMP后残余物及污染物的微电子装置清除所述残余物及污染物的时间,及将所述微电子装置并入到所述物品中。
在另一方面中,描述一种从上面具有CMP后残余物及污染物的微电子装置移除所述CMP后残余物及污染物的方法,所述方法包括:
用CMP浆料来抛光微电子装置;
使微电子装置与本文中所描述的清洁组合物接触达足以从微电子装置移除CMP后残余物及污染物的时间以形成含CMP后残余物的组合物;及
使微电子装置与含CMP后残余物的组合物持续接触达足以实现微电子装置的基本清洁的时间量。
另一方面涉及一种制造物品,所述制造物品包括清洁组合物、微电子装置及选自由残余物、污染物及其组合组成的群组的材料,其中所述清洁组合物包括至少一种季碱、至少一种胺、至少一种络合剂、任选地至少一种还原剂、任选地至少一种额外蚀刻剂、任选地至少一种清洁添加剂及水,且其中所述清洁组合物基本上没有碱金属氢氧化物、碱土金属氢氧化物及四甲基氢氧化铵,且所述残余物包括CMP后残余物、蚀刻后残余物及灰化后残余物中的至少一者。
另一方面涉及一种制造物品,所述制造物品包括清洁组合物、微电子装置及选自由残余物、污染物及其组合组成的群组的材料,其中所述清洁组合物包括至少一种胺、半胱氨酸、至少一种季碱、任选地至少一种额外螯合剂、任选地至少一种还原剂、任选地至少一种额外蚀刻剂、任选地至少一种清洁添加剂及水,其中所述组合物基本上没有碱金属氢氧化物、碱土金属氢氧化物及四甲基氢氧化铵,且所述残余物包括CMP后残余物、蚀刻后残余物及灰化后残余物中的至少一者。
实例1
如下文所展示制备五种溶液A-E。这些浓缩液经去离子水稀释后介于从约60:1到250:1的范围内。此后,铜及钴的蚀刻速率通过在25℃下将Co及Cu的PVD试片浸没在每一溶液中达30分钟而确定。
经确定,调配物D具有最低Co蚀刻速率。在不受理论束缚的情况下,认为,较低蚀刻速率可能是pH(介于从约10到约14的范围内)的结果及/或由以下引起的结果:存在半胱氨酸,从而准许形成CoO及/或Co氢氧化物层,而使Co金属钝化。在调配物E的情形中,Co蚀刻速率比调配物D高,但铜基本上是受保护的。
尽管本文中参考说明性实施例及特征已多方面地揭示本发明,但将了解,上文中所描述的实施例及特征并非用于限制本发明,且所属领域的技术人员基于本文中的揭示内容将联想到其它变化、修改及其它实施例。因此,本发明应广泛地解释为囊括在所附权利要求书的精神及范围内的所有此些变化、修改及替代实施例。
Claims (9)
1.一种用于清除来自微电子装置的残余物和/或污染物的组合物,其包括至少一种有机胺、至少一种溶剂、至少一种季碱和至少一种络合剂,其中所述组合物具有小于0.1wt.%的碱金属氢氧化物、碱土金属氢氧化物及四甲基氢氧化铵,且不含表面活性剂,
其中所述至少一种有机胺包括选自由以下各项组成的群组的物质:氨基乙基乙醇胺、N-甲氨基乙醇、氨基乙氧基乙醇、二甲基氨基乙氧基乙醇、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、异丙胺、2-氨基-1-丁醇、异丁醇胺、其它C1-C8烷醇胺、三乙烯二胺、乙二胺、己二胺、二乙烯三胺、三乙基胺、三甲基胺、1-甲氧基-2-氨基乙烷、二甘醇胺、吗啉及其组合,
其中所述至少一种溶剂为水,
其中所述至少一种季碱包括选自由以下各项组成的群组的物质:四乙基氢氧化铵TEAH、四丙基氢氧化铵TPAH、四丁基氢氧化铵TBAH、三丁基甲基氢氧化铵TBMAH、苄基三甲基氢氧化铵BTMAH、乙基三甲基氢氧化铵、胆碱氢氧化物、三(2-羟基乙基)甲基氢氧化铵、二乙基二甲基氢氧化铵、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及其组合,
其中所述至少一种络合剂为半胱氨酸,
其中所述半胱氨酸的量基于所述组合物的总重量介于从0.00005wt%到1wt%的范围内,
其中所述至少一种季碱的量基于所述组合物的总重量介于从5wt%到10wt%的范围内,以及
其中所述至少一种季碱:所述至少一种络合剂的重量百分比介于从50到300的范围内。
2.根据权利要求1所述的组合物,其中所述至少一种季碱包括胆碱氢氧化物。
3.根据前述任一权利要求所述的组合物,其进一步包括至少一种额外蚀刻剂,其中所述至少一种额外蚀刻剂选自由以下各项组成的群组:吗啉、二甘醇胺、3-丁氧基丙胺、丙二醇单丁醚、羟基乙基吗啉、羟基丙基吗啉、氨基乙基吗啉、氨基丙基吗啉、五甲基二乙烯三胺PMDETA、三甲基氨基乙基乙醇胺、三甲基氨基丙基乙醇胺及其组合。
4.根据权利要求3所述的组合物,其中所述至少一种额外蚀刻剂包括吗啉、二甘醇胺或吗啉与二甘醇胺的组合。
5.根据前述任一权利要求所述的组合物,其进一步包括至少一种清洁添加剂,其中所述至少一种清洁添加剂选自由以下各项组成的群组:羟基丙基纤维素、羟基乙基纤维素、羧基甲基纤维素、钠羧基甲基纤维素Na CMC、聚乙烯吡咯烷酮PVP、使用N-乙烯基吡咯烷酮单体制成的任何聚合物、聚丙烯酸酯及聚丙烯酸酯的类似物、聚丙氨酸、聚亮氨酸、聚甘氨酸、聚酰胺基羟基尿烷、聚内酯、聚丙烯酰胺、黄原胶、壳聚糖、聚环氧乙烷、聚乙烯醇、聚乙酸乙烯酯、聚丙烯酸、聚乙烯亚胺、山梨醇、木糖醇、脱水山梨醇的酯、仲醇乙氧基化物及其组合。
6.根据前述任一权利要求所述的组合物,其进一步包括至少一种还原剂,其中所述还原剂选自由以下各项组成的群组:抗坏血酸、L(+)-抗坏血酸、异抗坏血酸、抗坏血酸衍生物、没食子酸、甲脒亚磺酸、尿酸、酒石酸及其任何组合。
7.根据前述任一权利要求所述的组合物,其进一步包括选自由以下各项组成的群组的至少一种金属腐蚀抑制剂:腺苷、腺嘌呤、吡唑、1,2,4-三唑、1,2,3-三唑、咪唑、1H-吡唑-4-羧酸、3-氨基-5-叔丁基-1H-吡唑、5-氨基-1H-四唑、4-甲基吡唑、2-巯基苯并咪唑、2-氨基-5-(乙硫基)-1,3,4-噻二唑、2-氨基-5-乙基-1,3,4-噻二唑、其衍生物及其组合。
8.根据前述任一权利要求所述的组合物,其中所述半胱氨酸的量基于所述组合物的总重量介于从0.00005wt%到0.2wt%的范围内。
9.一种从上面具有残余物及污染物的微电子装置移除所述残余物及污染物的方法,所述方法包括使所述微电子装置与根据权利要求1到8中任一权利要求所述的组合物接触达足以从所述微电子装置至少部分地清除所述残余物及污染物的时间。
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