CN101434894A - 用于清洗半导体基质上无机残渣含有铜特效腐蚀抑制剂的含水清洗组合物 - Google Patents

用于清洗半导体基质上无机残渣含有铜特效腐蚀抑制剂的含水清洗组合物 Download PDF

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CN101434894A
CN101434894A CNA2008101788863A CN200810178886A CN101434894A CN 101434894 A CN101434894 A CN 101434894A CN A2008101788863 A CNA2008101788863 A CN A2008101788863A CN 200810178886 A CN200810178886 A CN 200810178886A CN 101434894 A CN101434894 A CN 101434894A
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acid
ammonium
cleaning agent
methyl
tetramethyl
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CN101434894B (zh
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威廉·A·沃伊特恰克
法蒂玛·玛·塞若
大卫·贝恩哈德
隆·阮
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Entegris Inc
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Advanced Technology Materials Inc
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Abstract

本发明涉及用于清洗半导体基质上无机残渣含有铜特效腐蚀抑制剂的含水清洗组合物，该半导体晶片清洗制剂，其含有按重量计为1－35％的氟化物源，按重量计为20－60％的有机胺，按重量计为0.1－40％的含氮组分如含氮羧酸或亚胺，按重量计为20－50％的水，及按重量计为0－21％的金属螯合剂。该制剂用于在抗蚀剂等离子体灰化步骤后从晶片上去除残渣，如从含有精细铜互连结构的半导体晶片上去除无机残渣。

Description

用于清洗半导体基质上无机残渣含有铜特效腐蚀抑制剂的含水清洗组合物
本申请为中国专利申请02820935.4(PCT/US02/33280)的分案申请。
相关申请
本申请要求于2001年3月3日申请的美国专利申请第09/818,073号的优先权，第09/818,073号要求于1997年8月29日申请的美国专利申请第08/924,021号的优先权，第08/924,021号要求于1997年4月25日申请的美国临时专利申请60/044,824号和于1997年1月9日申请的美国临时专利申请60/034,194的优先权。此外，本申请要求于2001年3月3日申请的在先美国专利申请第09/818,073号和于1997年8月29日申请的美国专利申请第08/924,021号的优先权并重复其实质部分。由于本申请中有一位发明人和在先申请中的相同，所以本申请是在先申请的部分连续申请。本申请将2001年3月3日申请的美国专利申请第09/818,073号、1997年8月29日申请的美国专利申请第08/924,021号、1997年4月25日申请的美国临时专利申请60/044,824号、1997年1月9日申请的美国临时专利申请60/034,194引为参考。
发明领域
本发明一般涉及半导体制造中所用的化学制剂，尤其涉及用于在抗蚀剂等离子体灰化步骤后从晶片上去除残渣的化学制剂。具体而言，本发明涉及用于从含有精细铜互连结构的半导体晶片上去除无机残渣的清洗制剂。
现有技术说明
现有技术公开了利用各种化学制剂以在抗蚀剂灰化步骤后去除残渣并清洗晶片。一些现有技术的化学制剂包括碱性组合物，其含有胺和/或氢氧化四烷基铵、水和/或其它溶液、及螯合剂。还有以含有氟化铵的酸性至中性溶液为基础的其它制剂。
各种现有制剂的缺点在于包括对金属和绝缘层不希望的去除，对所需要的金属层的腐蚀，尤其是对铜或铜合金部件而言。一些现有制剂利用腐蚀抑制添加剂以防止在清洗过程中不需要的铜金属腐蚀。然而，常规的腐蚀抑制添加剂通常对清洗过程具有有害的作用，这是由于这类添加剂可与残渣相互作用并抑制此残渣溶解进清洗液体中的原因。此外，清洗过程完成后，常规的添加剂不容易从铜表面冲洗掉。因此这种添加剂留在待清洗的表面上，从而引起集成电路污染。集成电路的污染物将不利地增加污染区域的电阻，并引起电路内不可预测的导电失效。
用于高级集成电路制造业如铜或钨互连材料的CMP后清洗机的制剂含有可加速物理清洗过程的浆料去除和残渣溶解组分。然而，这些常规的添加剂因为增加了电阻和腐蚀敏感性，因而通常对金属表面有有害的作用。
因此，本发明的一个目的是提供一种化学制剂，其在抗蚀剂灰化步骤后可有效地去除残渣，并且不会腐蚀和可能地剥离欲留在晶片上的精细结构。
本发明的另一个目的是用改进的腐蚀抑制剂代替常规的添加剂以保护半导体基质上的铜结构。
本发明的另一个目的是提供一种改进的腐蚀抑制剂，在残渣-去除过程完成后其可容易地用水或其它冲洗介质从基质冲洗掉，从而减少集成电路污染。
从下面的说明和所附的权利要求书中将更清楚本发明的其它特征和优点。
发明内容
本发明一般涉及半导体制造中所用的在抗蚀剂等离子体灰化步骤后从晶片上去除残渣的化学制剂。
在一方面，本发明涉及在晶片上的抗蚀剂等离子体灰化步骤后从该晶片上去除残渣的方法，包括使该晶片与清洗制剂接触，该制剂含有(i)氟化物源，(ii)至少一种有机胺，(iii)含氮羧酸或亚胺，(iv)水，及任选至少一种金属螯合剂。
本发明的另一方面涉及一种晶片清洗制剂，其含有(i)氟化物源，(ii)至少一种有机胺，(iii)含氮羧酸或亚胺，(iv)水，及任选至少一种金属螯合剂。
另一方面，本发明涉及一种等离子体灰化半导体制造后所用的半导体晶片清洗制剂，其含有如下重量百分数(按制剂的总重量计)的组分：
Figure A200810178886D00111
另一方面，本发明涉及一种用于化学机械研磨(CMP)后的清洗制剂，其是如上所列的晶片清洗制剂的稀释形式，其中稀释的制剂含有：(i)氟化物源，(ii)至少一种有机胺，(iii)70％～98％的水，及任选至少一种金属螯合剂和任选含氮羧酸或亚胺。
这种本发明的制剂可在等离子体灰化和/或CMP步骤后有效地去除残渣。
这种制剂也可在等离子体灰化后有效地去除金属卤化物和金属氧化物残渣，并有效地去除在CMP(化学机械研磨)后留下的氧化铝和其它氧化物浆料颗粒。
与含有氟化铵或胺的制剂相比，本发明的制剂可提供较好的剥离性能并且腐蚀性较小。与常规含胺的制剂相比，本发明的制剂在较低处理温度下也可提供较好的剥离性能。
本发明的制剂利用螯合剂以防止金属腐蚀并提高剥离效力，其中螯合剂可是单组分螯合剂或多组分螯合剂。
从下面的说明和所附的权利要求书中将更清楚本发明的其它特征和优点。
附图简要说明
图1示意性地表明在本发明的广义实施中所用的铜特效腐蚀抑制剂，其在铜金属上形成保护层以防止腐蚀；
图2示意性地表明铜特效腐蚀抑制剂由去离子水从铜表面洗掉；
图3表面本发明的清洗组分与表面的相互作用；
图4表明本发明的制剂可用于除去残渣和颗粒；
图5表明用浸渍方法所得结果的SEM；及
图6表明在互连材料上的材料蚀刻速率。
优选实施方案详细说明
本发明的制剂适用于剥离源于高密度等离子体蚀刻然后用含氧等离子体灰化的无机性晶片残渣。稀释形式的此类制剂也适用于CMP(化学机械研磨)后留下的氧化铝或其它氧化物浆料颗粒。
有利的是制剂含有(i)氟化物源，如氟化铵和/或氟化铵的衍生物，(ii)胺或胺混合物，(iii)含氮羧酸或亚胺，(iv)水，及任选和优选地，(v)一种或多种金属螯合剂。
本文中所用的氟化物源指可在水性清洗制剂中提供氟阴离子的化合物或化合物的混合物。
用于蚀刻后去除的优选制剂含有下面的组分，其重量百分数范围(按制剂的总重量计)也被表明：
Figure A200810178886D00131
用于CMP后清洗的优选制剂含有下面的组分，其重量百分数范围(按制剂的总重量计)也被表明：
Figure A200810178886D00132
本领域所属技术人员可以理解，如上所述的制剂组分可以是任何适合的类型或种类。对于制剂中的每一种成分而言，具体的示例性和优选的制剂组分在下面说明。
特别优选的胺包括下面中的一种或多种：
二甘醇胺(DGA)，
甲基二乙醇胺(MDEA)，
五甲基二亚乙基三胺(PMDETA)，
三乙醇胺(TEA)，及
三亚乙基二胺(TEDA)。
其它非常有效的胺包括：
六亚甲基四胺，
3，3-亚氨基双(N，N-二甲基丙胺)，
单乙醇胺
2-(甲氨基)乙醇，
4-(2-羟乙基)吗啉
4-(3-氨丙基)吗啉，及
N，N-二甲基-2-(2-氨乙氧基)乙醇。
用于本发明中的氟化物源包括氨气或氢氧化铵与氟化氢气体或氢氟酸的任何混合物。具体优选的氟化物源包括但不限于下面中的一种或多种：
氟化铵，及
氟化氢铵。
其它非常有效的氟化物源包括：
氟化三乙醇铵(TEAF)；
氟化二甘醇铵(DGAF)；
氟化甲基二乙醇铵(MDEAF)
氟化四甲基铵(TMAF)；及
三乙胺三(氟化氢)(TREAT-HF)。
具体优选的含氮羧酸和亚胺包括下面中的一种或多种：
亚氨基二乙酸(IDA)；
氨基乙酸；
氨三乙酸(NTA)；
1，1，3，3-四甲基胍(TMG)；及
羟乙基亚氨基二乙酸
乙二胺四乙酸(EDTA)。
可有效地用在本发明的制剂中的其它含氮羧酸或亚胺包括：
CH3C(＝NCH2CH2OH)CH2C(O)N(CH3)2
CH3C(＝NCH2CH2OCH2CH2OH)CH2C(O)N(CH3)2
CH3C(＝NH)CH2C(O)CH3
(CH3CH2)2NC(＝NH)N(CH3CH2)2
HOOCCH2N(CH3)2
HOOCCH2N(CH3)CH2COOH。
具体优选的金属螯合剂包括：
乙酰乙酰胺；
氨基甲酸铵；
吡咯烷二硫代氨基甲酸铵(APDC)；
丙二酸二甲酯；
乙酰乙酸甲酯；
N-甲基乙酰乙酰胺；
2，4-戊二酮；
硫代苯甲酸四甲铵；
1，1，1，5，5，5-六氟-2，4-戊二酮H(hfac)；
2，2，6，6-四甲基-3，5-庚二酮H(thd)；
三氟乙酸四甲铵；
二硫化四甲基秋兰姆(TMTDS)；
三氟乙酸；
乳酸；
乳酸铵；
丙二酸
甲酸，
乙酸，
丙酸，
γ-丁内酯，
三氟乙酸甲基二乙醇铵，及
三氟乙酸。
如上所述，与仅含有氟化铵或仅含有胺的制剂相比，氟化铵或取代的氟化物源与胺(不同与作为表面活性剂的以1％或更少的量存在的胺)的混合物可提供更好的剥离性能和较小的腐蚀性。此外，与常规含胺的制剂相比，生成的碱性溶液在较低温度下(例如21°-40℃)是有效的。
含氮羧酸和/或亚胺的存在能够使本发明的制剂在从含有精细铜结构的半导体基质表面上明显有效地剥离残渣。
含氮羧酸或亚胺能提供特别可与自由铜原子结合的官能团。如图1示意性地所示，在残渣-去除过程中可与铜表面接触的铜特效腐蚀抑制剂C将与铜表面结合并形成保护层以防止铜表面被清洗剂A+和X-腐蚀。
此外，如图2所示，铜特效腐蚀抑制剂可由去离子水或其它溶液很容易地洗掉，因此在清洗操作后在铜表面上剩下极少的污染物。
1，3-二羰基化合物作为螯合剂并防止金属腐蚀的用途是本发明制剂的特性，并可提高制剂的功效。
在各种现有制剂中，胺作为表面活性剂并占制剂的1％或更少，或者不被用作制剂成分。此外，现有制剂的特性是酸性的(pH<7)。在本发明的优选制剂中，胺作为制剂的主要组分，在剥离作用中是高度有效的，并使制剂具有碱性的pH特性(pH>7)。
除了特别举出的那些外，本发明的制剂可包括广范围的多种有机胺、取代的氟化铵及含氮羧酸。具有适宜特性的特定的取代的氟化铵包括通式R1R2R3R4NF所代表的那些，其中每个R基各自选自于氢和脂肪族基团。适合的含氮羧酸包括通式结构COOH-CH2-NRR’所代表的那些，其中R和R’中的每一个各自选自于氢、烷基、芳基及羧酸部分。适合的金属螯合剂包括通式结构X-CHR-Y所示的1，3-二羰基化合物。在此通式化合物中，R是氢原子或脂肪族基团，例如C1-C8烷基、芳基、烯基等。X和Y可以彼此相同或不同，并且都是含有具吸电子性质的多重键部分的官能团，例如CONH2、CONHR’、CN、NO2、SOR’或SO2Z，其中R’代表C1-C8烷基，Z代表另一个原子或基团，例如氢、卤或C1-C8烷基。
用在本发明组合物中的其它螯合剂包括通式R1R2R3R4N+-O2CCF3所示的三氟乙酸胺，其中R基中的每一个各自选自于氢和脂肪族基团，例如C1-C8烷基、芳基、烯基等。
根据本发明制剂最终的有效或所需用途，本发明的制剂也可选择性地含有诸如表面活性剂、稳定剂、腐蚀抑制剂、缓冲剂或共溶剂。
本发明的制剂特别适用于经过用含氯或含氟的等离子体蚀刻然后用氧等离子体灰化的晶片。此过程产生的残渣通常含有金属氧化物。在不引起金属和有效的装置性能所需要的氮化钛腐蚀的情况下，这种残渣经常难于完全溶解。此外，CMP后残余的金属氧化物和氧化硅浆料颗粒也能用本发明的制剂有效地除去。
通过下面的非限制性实施例可更全面地表明本发明的特征和优点。
实施例1
在两种不同类型的碱性清洗制剂中测试包含含有氢的羧酸或亚胺的铜特效腐蚀抑制剂，此制剂具有下面的成分和特性。
表1
Figure A200810178886D00181
通过标准四点探测技术确定铜蚀刻速率。如下表所示，本发明的腐蚀抑制剂的加入明显可降低铜蚀刻速率，并可有效地防止在清洗过程中所不需要的腐蚀：
Figure A200810178886D00182
实施例2
对含有亚氨基二乙酸抑制剂的制剂2进行污染物测试。待清洗的半导体晶片含有铜和硅薄膜。清洗操作完成后，晶片用25℃的去离子水浸渍约15分钟。得到的二次离子质谱数据如下；
Figure A200810178886D00191
上述结果表面铜氧化物CuxO可由清洗过程有效地除去，同时主要由清洗制剂中的有机腐蚀抑制剂引起的碳污染物也大减少。
在用于CMP后清洗金属表面如铜或钨表面的氧化硅或氧化铝的组合物中，本发明使用稀释的碱性氟化物。图3表面本发明的清洗组分怎样与表面相互作用。具体而言，图3表明在CMP过程后碱性氟化物30和螯合剂32溶解无机氧化物残渣34。
图4表明本发明的制剂可用于除去铜44表面的残渣40和颗粒42。在图4中颗粒42和残渣40与金属表面44及介电表面46接触。在CMP过程后会剩余颗粒42和残渣40。本发明的化学溶液可降低残渣和表面间的吸引力，并溶解铜氧化物和钨氧化物及氧卤化物。
已发现对从金属表面清洗残渣和浆料颗粒有效的制剂其pH约为3～11，但是通常pH值为约7～约9。这些制剂通常是含有氟化物源、有机胺和金属螯合剂的水性溶液。通常构成氟化物源和/或其衍生物的各个组分占制剂的约0.1～约5.0％，其中氟化物可以是本领域所属技术人员公知的多种此类氟化物源中的一种，氟化物源包括下面中的一种或多种：
氨气或氢氧化铵与氟化氢气体或氢氟酸的任何混合物；
氟化铵，
氟化氢铵；
氟化三乙醇铵(TEAF)；
氟化二甘醇铵(DGAF)；
氟化甲基二乙醇铵(MDEAF)
氟化四甲基铵(TMAF)；
三乙胺三(氟化氢)(TREAT-HF)。
有机胺或两种胺的混合物通常占本发明制剂的约1％～约15％，其中有机胺可以是本领域所属技术人员公知的多种此类有机胺中的一种，包括：
二甘醇胺(DGA)，
甲基二乙醇胺(MDEA)，
五甲基二亚乙基三胺(PMDETA)，
三乙醇胺(TEA)，
三亚乙基二胺(TEDA)，
六亚甲基四胺，
3，3-亚氨基双(N，N-二甲基丙胺)，
单乙醇胺，
2-(甲氨基)乙醇，
4-(2-羟乙基)吗啉，
4-(3-氨丙基)吗啉，及
N，N-二甲基-2-(2-氨乙氧基)乙醇。
混合物的含氮组分通常占混合物的0～约10％，其中含氮组分可以是本领域所属技术人员公知的多种此类含氮组分源中的一种，含氮组分源包括下面中的一种或多种：
亚氨基二乙酸(IDA)，
氨基乙酸，
氨三乙酸(NTA)，
羟乙基亚氨基二乙酸，
1，1，3，3-四甲基胍(TMG)，
乙二胺四乙酸(EDTA)，
CH3C(＝NCH2CH2OH)CH2C(O)N(CH3)2，
CH3C(＝NCH2CH2OCH2CH2OH)CH2C(O)N(CH3)2，
CH3C(＝NH)CH2C(O)CH3，
(CH3CH2)2NC(＝NH)N(CH3CH2)2，
HOOCCH2N(CH3)2，及
HOOCCH2N(CH3)CH2COOH。
金属螯合剂或螯合剂的混合物通常占制剂的约0～约5.0％。通常金属螯合剂可以是本领域所属技术人员公知的多种此类金属螯合剂中的一种，包括：
乙酰乙酰胺；
氨基甲酸铵；
吡咯烷二硫代氨基甲酸铵(APDC)；
丙二酸二甲酯；
乙酰乙酸甲酯；
N-甲基乙酰乙酰胺；
2，4-戊二酮；
1，1，1，5，5，5-六氟-2，4-戊二酮H(hfac)；
2，2，6，6-四甲基-3，5-庚二酮H(thd)；
硫代苯甲酸四甲铵；
三氟乙酸四甲铵；
二硫化四甲基秋兰姆(TMTDS)；
三氟乙酸；
乳酸；
乳酸铵；
丙二酸，
甲酸，
乙酸，
丙酸，
γ-丁内酯，
三氟乙酸甲基二乙醇铵，及
三氟乙酸。
几个代表性的制剂实施例是：
三乙醇胺                    4.5％
氟化铵                      0.5％
水                          95％
PMDETA                      3.8-4.5％
氟化铵                      0.5％
2，4-戊二酮                 1％
水                          94-94.7％
TEA                         1.7％
PMDETA                      1.5％
TEAF                        2％
亚氨基二乙酸                0.4％
氟化氢铵                    0.5％
水                          93.9％
TEA                         3.5％
PMDETA                      1.5％
2，4-戊二酮                 1.35％
氟化铵                      1.2％
水                          92.45％
TEA                        7％
PMDETA                     3％
2，4-戊二酮                2.7％
氟化铵                     2.4％
水                         84.9％
晶片可以浸渍在化学物质的溶液中，或通过喷射或者通过刷洗体系将化学物质涂敷在晶片表面。图5表明用标准浸渍方法所得结果的SEM。具体而言，图5表明在用氧化铝浆料CMP并在制剂c中于30℃下浸渍10分钟后的钨插头。此外，对外露材料的选择性可由蚀刻速率数据表明。图6和表3表明对含有电镀铜薄膜的互连材料的材料蚀刻速率。
Figure A200810178886D00231
尽管本文结合具体特征、形式和实施方案说明了本发明，但可以理解本发明不应由此限制。因此，本发明可以根据成分和最终用途的相应变化而以多种组合物来相应地实施。从而应该理解本发明包括在下面所保护的本发明精神和范围内的所有此类变化、修改及变更的实施方案。

Claims (24)

1.一种清洗制剂，包括至少一种有机胺、氟化物源和基于所述制剂总重量计为70wt.％～98wt.％的水，其中该清洗制剂的pH为7-9。
2.一种清洗制剂，其包括(a)氟化物源、(b)有机胺、(c)含氮组分和(d)水，其中，所述含氮组分包括选自如下的物质：亚氨基二乙酸，氨基乙酸，氨三乙酸，羟乙基亚氨基二乙酸，1，1，3，3-四甲基胍，CH3C(＝NCH2CH2OH)CH2C(O)N(CH3)2，CH3C(＝NCH2CH2OCH2CH2OH)CH2C(O)N(CH3)2，CH3C(＝NH)CH2C(O)CH3，(CH3CH2)2NC(＝NH)N(CH3CH2)2，HOOCCH2N(CH3)2，和HOOCCH2N(CH3)CH2COOH。
3.如权利要求2所述的清洗制剂，其中所述的氟化物源包括选自如下的氟化物：
氟化氢铵，
氟化铵，
氟化三乙醇铵TEAF，
氟化二甘醇铵DGAF，
氟化四甲基铵TMAF，
氟化甲基二乙醇铵MDEAF，和
三乙胺三(氟化氢)TREAT-HF。
4.如权利要求2所述的清洗制剂，其中所述有机胺包括选自如下的胺：
二甘醇胺DGA，
甲基二乙醇胺MDEA，
五甲基二亚乙基三胺PMDETA，
三乙醇胺TEA，
三亚乙基二胺TEDA，
六亚甲基四胺，
3，3-亚氨基双(N，N-二甲基丙胺)，
单乙醇胺，
2-(甲氨基)乙醇，
4-(2-羟乙基)吗啉，
4-(3-氨丙基)吗啉，和
N，N-二甲基-2-(2-氨乙氧基)乙醇。
5.如权利要求2所述的清洗制剂，其包括至少一种选自如下的金属螯合剂：
乙酰乙酰胺，
氨基甲酸铵，
吡咯烷二硫代氨基甲酸铵APDC，
丙二酸二甲酯，
乙酰乙酸甲酯，
N-甲基乙酰乙酰胺，
2，4-戊二酮，
1，1，1，5，5，5-六氟-2，4-戊二酮，
2，2，6，6-四甲基-3，5-庚二酮，
硫代苯甲酸四甲铵，
三氟乙酸四甲铵，
二硫化四甲基秋兰姆TMTDS，
三氟乙酸，
乳酸，
乳酸铵，
丙二酸，
甲酸，
乙酸，
丙酸，
γ-丁内酯，
三氟乙酸甲基二乙醇铵，和
三氟乙酸。
6.如权利要求2所述的清洗制剂，其中所述的氟化物源包括通式为R1R2R3R4NF的化合物，其中R1、R2、R3和R4各自独立地选自于氢原子和脂肪族基团，及其中所述的制剂含有如下通式的金属螯合剂：
X-CHR-Y，
其中R是氢、C1-C8烷基、芳基或烯基基团，并且X和Y是含有具有吸电子性质的多重键部分的官能团，其中各个X和Y独立地选自CONH2、CONHR’、CN、NO2、SOR’及SO2Z，其中R’是C1-C8烷基，Z是氢、卤或C1-C8烷基。
7.如权利要求2所述的清洗制剂，其中所述的氟化物源包括通式为R1R2R3R4NF的化合物，其中R1、R2、R3和R4独立地是氢或脂肪族基团，及其中所述的制剂包括通式为R1R2R3R4N+ -O2CCF3的金属螯合剂，其中R1、R2、R3和R4各自独立为氢、C1-C8烷基、芳基或烯基基团。
8.如权利要求2所述的清洗制剂，其中所述的氟化物源包括氨气或氢氧化铵与氟化氢气体或氢氟酸的任意组合。
9.如权利要求2所述的清洗制剂，其中所述制剂包括三乙醇胺、TEAF、PMDETA、亚氨基二乙酸、氟化氢铵和水。
10.如权利要求2所述的清洗制剂，其中所述组分基于这些组分总重量存在的重量百分数范围如下所示：
        氟化物源                  1-35％
         有机胺                   20-60％
选自含氮羧酸和亚胺的含氮组分    0.1-40％和
           水                   20-50％。
11.如权利要求2所述的清洗制剂，其还包括金属螯合剂。
12.如权利要求11所述的清洗制剂，其中所述螯合剂基于所述制剂的总重量存在的量为最高至21wt％。
13.一种从基片上去除残渣的方法，所述方法包括使所述基片与清洗制剂接触，所述清洗制剂包括(i)氟化物源，(ii)至少一种有机胺，(iii)含氮羧酸或亚胺，和(iv)水，其中，所述含氮组分包括选自如下的物质：亚氨基二乙酸，氨基乙酸，氨三乙酸，羟乙基亚氨基二乙酸，1，1，3，3-四甲基胍，CH3C(＝NCH2CH2OH)CH2C(O)N(CH3)2，CH3C(＝NCH2CH2OCH2CH2OH)CH2C(O)N(CH3)2，CH3C(＝NH)CH2C(O)CH3，(CH3CH2)2NC(＝NH)N(CH3CH2)2，HOOCCH2N(CH3)2，和HOOCCH2N(CH3)CH2COOH。
14.如权利要求13所述的方法，其中所述的氟化物源包括选自如下的氟化物：
氟化铵，
氟化氢铵，
氟化三乙醇铵TEAF，
氟化二甘醇铵DGAF，
氟化甲基二乙醇铵MDEAF，
氟化四甲基铵TMAF，和
三乙胺三(氟化氢)TREAT-HF。
15.如权利要求13所述的方法，其中所述的有机胺包括选自如下的胺：
二甘醇胺DGA，
甲基二乙醇胺MDEA，
五甲基二亚乙基三胺PMDETA，
三乙醇胺TEA，
三亚乙基二胺TEDA，
六亚甲基四胺，
3，3-亚氨基双(N，N-二甲基丙胺)，
单乙醇胺，
2-(甲氨基)乙醇，
4-(2-羟乙基)吗啉，
4-(3-氨丙基)吗啉，和
N，N-二甲基-2-(2-氨乙氧基)乙醇。
16.如权利要求13所述的方法，包括至少一种选自如下的金属螯合剂：
乙酰乙酰胺，
氨基甲酸铵，
吡咯烷二硫代氨基甲酸铵APDC，
丙二酸二甲酯，
乙酰乙酸甲酯，
N-甲基乙酰乙酰胺，
2，4-戊二酮，
1，1，1，5，5，5-六氟-2，4-戊二酮，
2，2，6，6-四甲基-3，5-庚二酮，
硫代苯甲酸四甲铵，
三氟乙酸四甲铵，
二硫化四甲基秋兰姆TMTDS，
三氟乙酸，
乳酸，
乳酸铵，
丙二酸，
甲酸，
乙酸，
丙酸，
γ-丁内酯，
三氟乙酸甲基二乙醇铵，和
三氟乙酸。
17.如权利要求13所述的方法，其中所述清洗制剂包括三乙醇胺、TEAF、PMDETA、亚氨基二乙酸、氟化氢铵和水。
18.如权利要求13所述的方法，该方法在使所述基片与所述清洗制剂接触之前，还包括从所述基片的表面等离子体蚀刻金属化层，和从所述基片的表面等离子体灰化抗蚀剂。
19.如权利要求13所述的方法，其中所述清洗制剂的组分基于这些组分总重量存在的重量百分数范围如下所示：
         氟化物源                     1-35％
          有机胺                      20-60％
选自含氮羧酸和亚胺的含氮组分        0.1-40％和
            水                      20-50％。
20.如权利要求13所述的方法，其中所述清洗制剂还包括金属螯合剂。
21.如权利要求20所述的方法，其中所述螯合剂基于所述制剂的总重量存在的量为最高至21wt％。
22.一种清洗制剂，其包括(a)氟化物源、(b)有机胺、(c)含氮组分、(d)水和(e)任选的金属螯合剂，其中，所述含氮组分包括选自如下的物质：氨基乙酸，氨三乙酸，羟乙基亚氨基二乙酸，1，1，3，3-四甲基胍，CH3C(＝NCH2CH2OH)CH2C(O)N(CH3)2，CH3C(＝NCH2CH2OCH2CH2OH)CH2C(O)N(CH3)2，CH3C(＝NH)CH2C(O)CH3，(CH3CH2)2NC(＝NH)N(CH3CH2)2，HOOCCH2N(CH3)2，和HOOCCH2N(CH3)CH2COOH。
23.如权利要求22所述的清洗制剂，其包括至少一种选自如下物质的金属螯合剂：
乙酰乙酰胺，
氨基甲酸铵，
吡咯烷二硫代氨基甲酸铵APDC，
丙二酸二甲酯，
乙酰乙酸甲酯，
N-甲基乙酰乙酰胺，
2，4-戊二酮，
1，1，1，5，5，5-六氟-2，4-戊二酮，
2，2，6，6-四甲基-3，5-庚二酮，
硫代苯甲酸四甲铵，
三氟乙酸四甲铵，
二硫化四甲基秋兰姆TMTDS，
三氟乙酸，
乳酸，
乳酸铵，
丙二酸，
甲酸，
乙酸，
丙酸，
γ-丁内酯，
三氟乙酸甲基二乙醇铵，和
三氟乙酸。
24.如权利要求22所述的清洗制剂，其中所述清洗制剂包括三乙醇胺、TEAF、PMDETA、亚氨基二乙酸、氟化氢铵和水。
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