CN115485417A - 蚀刻钼的方法及组合物 - Google Patents
蚀刻钼的方法及组合物 Download PDFInfo
- Publication number
- CN115485417A CN115485417A CN202180032467.2A CN202180032467A CN115485417A CN 115485417 A CN115485417 A CN 115485417A CN 202180032467 A CN202180032467 A CN 202180032467A CN 115485417 A CN115485417 A CN 115485417A
- Authority
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- China
- Prior art keywords
- acid
- etchant composition
- hydroxide
- ether
- ammonium
- Prior art date
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- Pending
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- LUVHDTDFZLTVFM-UHFFFAOYSA-M tetramethylazanium;chlorate Chemical compound [O-]Cl(=O)=O.C[N+](C)(C)C LUVHDTDFZLTVFM-UHFFFAOYSA-M 0.000 claims description 2
- FDXKBUSUNHRUIZ-UHFFFAOYSA-M tetramethylazanium;chlorite Chemical compound [O-]Cl=O.C[N+](C)(C)C FDXKBUSUNHRUIZ-UHFFFAOYSA-M 0.000 claims description 2
- ZRVXFJFFJZFRLQ-UHFFFAOYSA-M tetramethylazanium;iodate Chemical compound [O-]I(=O)=O.C[N+](C)(C)C ZRVXFJFFJZFRLQ-UHFFFAOYSA-M 0.000 claims description 2
- ZCWKIFAQRXNZCH-UHFFFAOYSA-M tetramethylazanium;perchlorate Chemical compound C[N+](C)(C)C.[O-]Cl(=O)(=O)=O ZCWKIFAQRXNZCH-UHFFFAOYSA-M 0.000 claims description 2
- HLQAWDQQEJSALG-UHFFFAOYSA-M tetramethylazanium;periodate Chemical compound C[N+](C)(C)C.[O-]I(=O)(=O)=O HLQAWDQQEJSALG-UHFFFAOYSA-M 0.000 claims description 2
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Classifications
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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
- H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
- H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic Table or AIIIBV compounds with or without impurities, e.g. doping materials
- H01L21/30—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26
- H01L21/31—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26 to form insulating layers thereon, e.g. for masking or by using photolithographic techniques; After treatment of these layers; Selection of materials for these layers
- H01L21/3205—Deposition of non-insulating-, e.g. conductive- or resistive-, layers on insulating layers; After-treatment of these layers
- H01L21/321—After treatment
- H01L21/3213—Physical or chemical etching of the layers, e.g. to produce a patterned layer from a pre-deposited extensive layer
- H01L21/32133—Physical or chemical etching of the layers, e.g. to produce a patterned layer from a pre-deposited extensive layer by chemical means only
- H01L21/32134—Physical or chemical etching of the layers, e.g. to produce a patterned layer from a pre-deposited extensive layer by chemical means only by liquid etching only
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
- C23F1/00—Etching metallic material by chemical means
- C23F1/10—Etching compositions
- C23F1/14—Aqueous compositions
- C23F1/32—Alkaline compositions
- C23F1/38—Alkaline compositions for etching refractory metals
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Abstract
本发明描述一种用于以一定蚀刻速率,从微电子装置蚀刻钼的蚀刻剂组合物及方法。使微电子装置与蚀刻剂组合物接触足以至少部分去除所述钼的时间。所述蚀刻剂组合物包含至少一种氧化剂、至少一种氧化剂稳定剂及至少一种碱且具有7.5到13的pH。所述蚀刻剂组合物以5到
Description
技术领域
背景技术
通常,使用钨及基于钨的材料作为3D-NAND制造中的电极。然而,已发现钨材料对各种蚀刻剂组合物敏感。例如,在使用W电极的工艺中,发现用于电极绝缘的包括磷酸及硝酸的酸性组合物(所谓的“W凹槽”)引起钨层的部分蚀刻。
目前,3D-NAND结构在内存装置中发现实用性。为在内存性能中实现较佳效用,3D-NAND制造商已研究在内存装置中可导致极佳性能的其它材料。具体来说,许多3D-NAND制造商已用钼替换W层。因此,制造商需可选择性去除凹槽中的Mo而不去除TiN的蚀刻剂组合物。可以一定蚀刻速率选择性去除钼,使得各凹槽在可控蚀刻条件下实现大体上相同的目标蚀刻深度的蚀刻剂组合物特别受关注。
发明内容
本发明大体上涉及一种用于从微电子装置选择性去除钼的蚀刻剂组合物及方法。有利地,所述蚀刻剂组合物以足以在3D-NAND装置的含Mo凹槽中高效且有效实现大体上一致蚀刻深度的蚀刻速率去除钼。
在一个实施例中,本发明涉及一种用于去除钼的蚀刻剂组合物。所述组合物包含至少一种氧化剂、至少一种氧化剂稳定剂、至少一种碱,及水。所述蚀刻剂组合物不含氨或氢氧化铵且具有7.5到12的pH。在此pH下,及在包括氧化剂稳定剂的情况下,所述蚀刻剂组合物以5到的蚀刻速率去除钼。
在另一实施例中,本发明涉及一种以目标蚀刻速率从微电子装置去除钼的方法。所述方法包括使所述微电子装置与蚀刻剂组合物接触足以从所述微电子装置至少部分去除钼的时间。所述蚀刻剂组合物包含至少一种氧化剂、至少一种氧化剂稳定剂、至少一种碱及水。所述蚀刻剂组合物不含氨或氢氧化铵且具有7.5到12的pH。所述方法又包括以5到的蚀刻速率蚀刻钼。
从随后的公开内容及随附权利要求书将更完全显而易见其它方面、特征及优点。已发现此蚀刻剂组合物可实现钼的足够可控蚀刻而不过度蚀刻,而同时提供选择性以在其它金属组分(特别TiN)的存在下去除钼。此兼容性及蚀刻控制在(例如)3D-NAND装置的制造中具有相当大的益处。
具体实施方式
本发明大体上涉及适用于从具有钼及含钼材料的微电子装置去除这些材料的水性或半水性组合物。所述组合物特别适用于在TiN的存在下选择性去除钼。
为便于参考,“微电子装置”对应于经制造以用于微电子、集成电路、能量收集或计算机芯片应用中的半导体衬底、平面显示器、相变内存装置、太阳电池板及包括太阳电池装置、光伏打及微机电系统(MEMS)的其它产品。特别优选的微电子是3D-NAND装置。应了解,术语“微电子装置”、“微电子衬底”及“微电子装置结构”不希望以任何方式限制且包括将最终变为微电子装置或微电子组合件的任何衬底或结构。
微电子装置包含含钼材料。如本文使用,基于材料的总重量,“含钼材料”及“钼”包括包含大于50重量%元素钼的任何材料。含钼材料的实例包括(但不限于)纯钼(Mo)及合金或含有钼的混合物。例如,已知在制造微电子装置期间沉积的钼也可含有铝(Mo-Al)或钛(Mo-Ti),一般少于5重量%,及“钼”将包括这些材料。所属领域的技术人员应了解,各种钼物质的化学式可基于钼离子的氧化态变化,其中钼的常见氧化态为-3、-1、+1、+2、+3、+4、+5或+6。
如本文使用,“氮化钛”及“TiNx”对应于纯氮化钛及包括变化的化学计量,及含氧量(TiOxNy)的不纯氮化钛。
如本文定义,“低k电介质材料”对应于用作层状微电子装置中的电介质材料的任何材料,其中所述材料具有小于约3.5的电介质常数。优选地,所述低k电介质材料包括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物(CDO)玻璃。应知晓所述低k电介质材料可具有变化的密度及变化的孔隙率。
如本文定义,“金属导体层”或“金属层”包含铜、钨、钴、铝、钌,包含它们的合金,及其组合。
“大体上不含”在本文中定义为小于2重量%,优选小于1重量%,更优选小于0.5重量%,及最优选小于0.1重量%。在一个实施例中,“大体上不含”对应于零百分比,指示所述组合物不含特定组分。
如本文使用,“约”希望对应于规定值的±5%。
如下文中更充分描述,本文描述的组合物可以多种具体调配物体现。
在所有这些组合物中,其中所述组合物的具体组分是参考包括零下限的重量百分比范围加以讨论,应了解所述组合物的各种具体实施例中可存在或缺乏这些组分,且在存在这些组分的情况下,基于其中采用这些组分的组合物的总重量,所述组分可以低到0.001重量%的浓度存在。
在整个本说明书的描述及权利要求书中,措辞“包含(comprise)”及“含有”及所述措辞的变化例如“包含(comprising)”及“包含(comprises)”表示“包括(但不限于)”且不排除其它组分、整数或步骤。然而,使用所述措辞“包含”的所有地方,也明确包含其中将“包含”解读成“由……构成”或“基本上由……构成”的实施例。
本文中,除非上下文另有要求,否则单数包含复数。具体来说,在使用不定冠词的情况下,除非上下文另有要求,否则本说明书应了解为考虑复数及单数。
本发明的各方面的优选特征可结合其它方面中的任一者描述。在本申请案的范围内,明确预期,前述段落、权利要求书及/或下列说明书及图式中阐述的各种方面、实施例、实例及替代方案及具体来说其个别特征可独立地或以任何组合使用。也就是说,所有实施例及/或任何实施例的特征可以任何方式及/或组合进行组合,除非这些特征不兼容。
本发明涉及一种用于从微电子装置,特别从所述装置的高纵横比区域选择性去除钼的蚀刻剂组合物及方法。用于此装置的典型基于水的钼蚀刻剂组合物已包括氧化剂且已维持在低pH(也就是说,小于7)下。发明人在大量研究后确定,在这些酸性氧化条件下,将待去除的钼区域氧化为MoOx(例如MoO4 -2)。基于相图分析,确定使这些物质有效溶解于水性酸性组合物中非常困难,导致蚀刻速率降低。水性碱性调配物将是优选的,以有效去除氧化钼层或防止形成氧化钼层。然而,在高pH条件下,预期许多氧化剂(包括过氧化氢)将分解,此减少可用氧化剂的量,且相应地,降低蚀刻剂组合物的有效性。
因此,为从微电子装置可控蚀刻基于钼的材料,本发明的一个实施例涉及一种包含至少一种氧化剂、至少一种氧化剂稳定剂及至少一种碱,由它们构成或基本上由它们构成的蚀刻剂组合物。所述蚀刻剂组合物可为水性或半水性且具有7.5到13的pH。已意外发现,高pH蚀刻剂组合物中包括氧化剂稳定剂防止氧化剂显著分解并提供以可控制在5到之间的蚀刻速率从微电子装置的高纵横比区域去除钼的高效且有效组合物。以大于的蚀刻速率去除Mo的蚀刻剂组合物将非所欲的,特别对于高纵横比区域(这些具有3D-NAND结构的凹槽),因为难以控制实现一致地从各凹槽去除Mo及所需蚀刻深度(例如20到30nm)。小于的蚀刻速率将需显著更长的蚀刻时间,这将导致3D-NAND制造工艺低效。优选地,钼蚀刻速率为10到且更优选10到
本发明的蚀刻剂组合物中的至少一种氧化剂可为任何可氧化钼以产生组合物可溶性钼物质,优选在碱性pH条件下可溶的物质。合适氧化剂的实例包括(但不限于)过氧化氢(H2O2)、FeCl3、FeF3、Fe(NO3)3、Sr(NO3)2、CoF3、MnF3、过一硫酸氢钾(oxone)、(2KHSO5·KHSO4·K2SO4)、硝酸(HNO3)、过氧单硫酸氢铵、亚氯酸铵(NH4ClO2)、氯酸铵(NH4ClO3)、碘酸铵(NH4IO3)、硝酸铵(NH4NO3)、过硼酸铵(NH4BO3)、过氯酸铵(NH4ClO4)、过碘酸铵(NH4IO4)、过硫酸铵((NH4)2S2O8)、次氯酸铵(NH4ClO)、钨酸铵((NH4)10H2(W2O7))、过硫酸钠(Na2S2O8)、次氯酸钠(NaClO)、过硼酸钠、碘酸钾(KIO3)、过锰酸钾(KMnO4)、过硫酸钾(K2S2O8)、次氯酸钾(KClO)、四甲基亚氯酸铵((N(CH3)4)ClO2)、四甲基氯酸铵((N(CH3)4)ClO3)、四甲基碘酸铵((N(CH3)4)IO3)、四甲基过硼酸铵((N(CH3)4)BO3)、四甲基过氯酸铵((N(CH3)4)ClO4)、四甲基过碘酸铵((N(CH3)4)IO4)、四甲基过硫酸铵((N(CH3)4)S2O8)、四丁基过氧单硫酸氢铵、过氧单硫酸、过氧化氢脲((CO(NH2)2)H2O2)、过乙酸(CH3(CO)OOH)、叔丁基过氧化氢、硝基苯磺酸盐、1,4-苯醌、甲醌、二甲基-1,4-苯醌、氯醌(chloranil)、四氧嘧啶(alloxan)、过碘酸,及其组合。较佳地,所述氧化剂包含过氧化氢、过氧化氢脲、过硫酸铵、过碘酸、过乙酸或叔丁基过氧化氢。
氧化剂的含量可为有效从微电子装置去除钼(特别在其它金属层的存在下)的任何量。具体来说,所述蚀刻剂组合物可包含约0.1重量%到约5重量%的氧化剂。优选地,氧化剂的量是约0.1重量%到约2重量%,且更优选地,约0.1到约1重量%。在与微电子装置接触前,所述氧化剂可直接引入组合物内或可制备成氧化剂溶液的一部分,并接着与其余组分组合。后者通过将暴露于碱性条件的时间量最小化,又防止所述氧化剂分解。
蚀刻剂组合物又包含至少一种碱以使所述组合物的pH实现至少7.5。优选地,所述组合物的pH是7.5到13及更优选8到11。合适碱的实例包括(但不限于)碱金属氢氧化物、碱土金属氢氧化物、四烷基氢氧化铵(例如四甲基氢氧化铵(TMAH)、四乙基氢氧化铵(TEAH)、四丙基氢氧化铵(TPAH)及四丁基氢氧化铵(TBAH))、三丁基甲基氢氧化铵(TBMAH)、苯甲基三甲基氢氧化铵(BTMAH)、氢氧化胆碱、乙基三甲基氢氧化铵、三(2-羟乙基)甲基氢氧化铵、二乙基二甲基氢氧化铵、四烷基氢氧化磷(例如四丁基氢氧化磷(TBPH)、四甲基氢氧化磷、四乙基氢氧化磷及四丙基氢氧化磷)、苯甲基三苯基氢氧化磷、甲基三苯基氢氧化磷、乙基三苯基氢氧化磷、正丙基三苯基氢氧化磷,及其组合。优选地,所述碱包含TMAH或氢氧化胆碱。
本文描述的蚀刻剂组合物可及优选大体上不含氨或氢氧化铵。更优选地,所述蚀刻剂组合物不含氨及氢氧化铵。这些碱尽管有效使pH上升到所需水平,但存在严重健康及环境问题,且将显著增加处理及减轻这些问题的成本。
碱的含量可为有效提供及/或维持碱性pH水平的任何量。具体来说,蚀刻剂组合物可包含约0.1重量%到约10重量%的碱。优选地,碱的量是约0.1重量%到约8重量%,且更优选地,约0.1到约5重量%。
本发明的蚀刻剂组合物又包含至少一种氧化剂稳定剂。如本文使用,“氧化剂稳定剂”或“稳定剂”包括那些防止或减少氧化剂(例如过氧化氢)分解(此分解减少其作为氧化剂的有效性)的化合物。氧化剂稳定剂可在氧化剂前或与氧化剂组合添加到所述蚀刻剂组合物。合适的氧化剂稳定剂包括(但不限于)甘氨酸、丝氨酸、脯氨酸、亮氨酸、丙氨酸、天冬酰氨酸、天冬氨酸、谷酰氨酸、缬氨酸及赖氨酸、氮基三乙酸、亚氨基二乙酸、羟乙膦酸(etidronic acid)、乙二胺四乙酸(EDTA)、(1,2-亚环己基二氮基)四乙酸(CDTA)、尿酸、四乙二醇二甲醚、二乙三胺五乙酸、丙二胺四乙酸、乙二胺二琥珀酸、胺苯磺酰胺,及其组合。优选地,所述氧化剂稳定剂包含CDTA或EDTA。
不希望受任何理论束缚,据信氧化剂稳定剂有效去除或另外捕获由于去除钼材料产生的金属杂质。例如,如上文讨论,所述钼可包括少量(例如以ppm水平计)另外金属物质(例如Ti的Al)。已知这些金属引起氧化剂(例如过氧化氢),特别在高pH下分解。据信稳定剂结合这些金属,从而减少氧化剂降解的量。下文更详细讨论,出于这种原因,尽管所述稳定剂可以有效提供氧化剂的增加的稳定性及减少的分解的任何量存在,但所述氧化剂稳定剂一般以小于任何络合剂的量存在。例如,所述蚀刻剂组合物可包含约0.0001重量%到约1.0重量%的氧化剂稳定剂。优选地,稳定剂的量是约0.0005重量%到约0.5重量%,且更优选地,约0.001重量%到约0.1重量%。
除上文讨论的组分外,本发明的蚀刻剂组合物可进一步包含任选的另外组分,由它们构成,或基本上由它们构成,所述任选的另外组分的存在进一步改良及/或增强组合物从微电子装置选择性去除钼的性能。例如,所述蚀刻剂组合物可进一步包含至少一种金属腐蚀抑制剂、至少一种络合剂及/或至少一种溶剂。
金属腐蚀抑制剂可用于在去除钼层期间保护微电子装置上存在的金属层。所述金属腐蚀抑制剂可包含一种或多种腐蚀抑制剂,由其构成,或基本上由其构成,所述腐蚀抑制剂包括(但不限于)5-氨基四唑、5-苯基-苯并三唑、1H-四唑-5-乙酸、1-苯基-2-四唑啉-5-硫酮、苯并咪唑、甲基四唑、吡唑、5-氨基-1,3,4-噻二唑-2-硫醇(ATDT)、苯并三唑(BTA)、1,2,4-三唑(TAZ)、1,2,3-三唑、甲苯基三唑、5-甲基-苯并三唑(mBTA)、5-苯基-苯并三唑、5-硝基-苯并三唑、苯并三唑羧酸、3-氨基-5-巯基-1,2,4-三唑、1-氨基-1,2,4-三唑、羟基苯并三唑、2-(5-氨基-戊基)-苯并三唑、1-氨基-1,2,3-三唑、1-氨基-5-甲基-1,2,3-三唑、3-氨基-1,2,4-三唑(3-ATA)、3-巯基-1,2,4-三唑、3-异丙基-1,2,4-三唑、5-苯基硫醇-苯并三唑、卤基-苯并三唑(卤基=F、Cl、Br或I)、萘三唑、2-巯基苯并咪唑(MBI)、2-巯基苯并噻唑、4-甲基-2-苯基咪唑、2-巯基噻唑啉、5-氨基-1,2,4-三唑(5-ATA)、3-氨基-5-巯基-1,2,4-三唑、戊四唑、5-苯基-1H-四唑、5-苯甲基-1H-四唑、2,4-二氨基-6-甲基-1,3,5-三嗪、噻唑、三嗪、甲基四唑、1,3-二甲基-2-咪唑烷酮、1,5-五亚甲基四唑、1-苯基-5-巯基四唑、二氨基甲基三嗪、咪唑啉硫酮、4-甲基-4H-1,2,4-三唑-3-硫醇、4-氨基-4H-1,2,4-三唑、3-氨基-5-甲基硫基-1H-1,2,4-三唑、苯并噻唑、咪唑、吲唑、腺嘌呤、腺苷、咔唑,及其组合。优选地,所述金属腐蚀抑制剂包含甲苯基三唑。
任选的金属腐蚀抑制剂含量可为有效防止金属层腐蚀,尤其在高pH下,且不显著影响钼的蚀刻速率的任何量。因此,蚀刻剂组合物中腐蚀抑制剂的量是提供基本上抑制剂独立的Mo蚀刻速率的量。具体来说,当使用时,所述蚀刻剂组合物可包含约0.001重量%到约1.0重量%的腐蚀抑制剂。优选地,腐蚀抑制剂的量是约0.05重量%到约0.5重量%,且优选地,约0.01到约0.10重量%。
如本文使用,“络合剂”包括那些所属领域的技术人员了解为络合剂、螯合剂及/或钳合剂的化合物。络合剂将与待使用本文中描述的组合物从微电子装置去除的钼原子及/或离子化学组合或使其物理上保持,以改良此材料的蚀刻速率。合适的络合剂包括(但不限于)氨基乙基乙醇胺、N-甲基氨基乙醇、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(MEA)、三乙醇胺(TEA)、1-氨基-2-丙醇、2-氨基-1-丁醇、异丁醇胺、三乙二胺、4-(2-羟乙基)吗啉(HEM)、乙二胺四乙酸(EDTA)、间苯二甲胺(MXDA)、亚氨基二乙酸(IDA)、2-(羟乙基)亚氨基二乙酸(HIDA)、氮基三乙酸、硫脲、1,1,3,3-四甲基脲、脲、脲衍生物、尿酸、丙氨酸、精氨酸、天冬酰氨酸、天冬氨酸、半胱氨酸、谷氨酸、谷酰氨酸、组氨酸、异亮氨酸、亮氨酸、赖氨酸、甲硫氨酸、苯基丙氨酸、脯氨酸、丝氨酸、苏氨酸、色氨酸、酪氨酸、缬氨酸、1-羟基亚乙基-1,1-二膦酸(HEDP)、1,5,9-三氮杂环十二烷-N,N',N"-三(亚甲基膦酸)(DOTRP)、1,4,7,10-四氮杂环十二烷-N,N',N",N'"-四(亚甲基膦酸)(DOTP)、氮基三(亚甲基)三膦酸、二乙三胺五(亚甲基膦酸)(DETAP)、氨基三(亚甲基膦酸)、双(六亚甲基)三胺五亚甲基膦酸、1,4,7-三氮杂环壬烷-N,N',N"-三(亚甲基膦酸(NOTP)、羟乙基二膦酸盐、氮基三(亚甲基)膦酸、2-膦酰基-丁烷-1,2,3,4-四羧酸、羧乙基膦酸、氨基乙基膦酸、草甘膦、乙二胺四(亚甲基膦酸)苯基膦酸、草酸、琥珀酸、马来酸、苹果酸、丙二酸、己二酸、邻苯二甲酸、乳酸、柠檬酸、柠檬酸钠、柠檬酸钾、柠檬酸铵、丙三羧酸、三羟甲基丙酸、酒石酸、葡萄糖醛酸、2-羧基吡啶、4,5-二羟基-1,3-苯二磺酸二钠盐,及其组合。优选地,所述络合剂包含1-羟基亚乙基-1,1-二膦酸(HEDP)、乳酸或柠檬酸。
任选的络合剂含量可为有效改良钼的蚀刻速率的任何量。例如,当使用蚀刻剂组合物时,其可包含约0.1重量%到约20重量%的络合剂。优选地,络合剂的量是约0.5重量%到约15重量%,且更优选地,约1.0到约10重量%。
如上文讨论,本发明蚀刻剂组合物可为水性组合物或可为半水性组合物。因此,在一些实施例中,所述蚀刻剂组合物包含水而无另外溶剂,而在其它实施例中,所述蚀刻剂组合物进一步包含水及至少一种水溶性或水混溶性有机溶剂。包括至少一种溶剂与水的组合可以另外改良所述蚀刻剂组合物,例如改良所得蚀刻钼表面的平面性。合适溶剂包括(例如)甲醇、乙醇、异丙醇、丁醇、戊醇、己醇、2-乙基-1-己醇、庚醇、辛醇、乙二醇、丙二醇、丁二醇、碳酸丁烯酯、碳酸乙烯酯、碳酸丙烯酯、二丙二醇、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、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、丙二醇正丁基醚、二丙二醇正丁基醚、三丙二醇正丁基醚、丙二醇苯醚、2,3-二氢十氟戊烷、乙基全氟丁基醚、甲基全氟丁基醚、碳酸烷基酯、碳酸伸烷基酯、4-甲基-2-戊醇,及其组合。优选地,所述至少一种溶剂包含丙二醇。当使用溶剂时,其含量可占总溶剂的约10重量%到约90重量%,优选总溶剂的约30重量%到约85重量%,及更优选总溶剂的约50重量%到约85重量%的量,其余为水。
在本发明的蚀刻剂组合物的一实施例中,所述组合物包含至少一种氧化剂、至少一种氧化剂稳定剂、至少一种碱及水,由它们构成,或基本上由它们构成,以所述组合物总重量计,其含量在以下列范围:
将知晓常见实务为制造使用前待稀释的组合物的浓缩形式。例如,所述组合物可以更浓缩的形式制造且此后在工厂处使用前及/或期间,在制造商处用至少一种溶剂稀释。稀释比率可在约0.1份稀释剂:1份组合物浓缩物到约100份稀释剂:1份组合物浓缩物的范围内。应进一步知晓,本文描述的组合物包括可经时不稳定的氧化剂。因此,所述浓缩形式可大体上不含氧化剂且可在工厂处使用前及/或期间,由制造商将所述氧化剂引入所述浓缩或稀释的组合物内。
本文描述的蚀刻剂组合物易通过简单添加个别组分并混合到均质条件来调配。此外,所述组合物可容易调配成在使用时或使用前混合的单包装调配物或多部分调配物,优选多部分调配物。所述多部分调配物的个别部分可于工具处或在混合区域/范围(例如在线混合器)中或在所述工具上游的储存槽中混合。经考虑,所述多部分调配物的各种部分可含有当混合在一起时形成所需组合物的组分/成分的任何组合。个别组分的浓度可在组合物的具体倍数内广泛变化,也就是说,更稀或更浓,且应知晓所述组合物可不同且替代地包含与本文公开内容一致的组分的任何组合,由它们构成或基本上由它们构成。
实例
蚀刻剂组合物是通过使用TEAH作为滴定仪将氧化剂及络合剂组合调节到目标pH来制备。在室温下将所述混合物搅拌15min以提供澄清溶液。
在30℃下将具有Mo层的试片在含有组合物的浴中放置15min。测量去除的Mo的量,且还测定这些组合物的TiN蚀刻速率。
蚀刻剂组合物及它们相应的蚀刻速率显示于下表1中。
表1
这些组合物中的每一者包括1重量%的氧化剂及0.01重量%的CDTA作为氧化剂稳定剂。
如显示,这些蚀刻剂组合物(它们包含至少一种氧化剂、至少一种氧化剂稳定剂及至少一种碱,调节到7.5到13,优选8到11的pH)中的每一者以5到的蚀刻速率可控去除钼。另外,相应的TiN蚀刻速率非常低,证实所述蚀刻剂组合物去除Mo的选择性。
尽管本文已参考说明性实施例及特征不同地公开本发明,但应知晓上文中描述的实施例及特征无意限制本发明,且基于本文公开内容,所属领域的一般技术人员应知晓其它变化、修饰及其它实施例。因此,本发明应广义地解释为包含于下文阐述的随附申请专利范围的精神及范围内的所有这些变化、修饰及替代实施例。
Claims (20)
1.一种从微电子装置去除钼的蚀刻剂组合物,所述蚀刻剂组合物包含:
至少一种氧化剂;
至少一种氧化剂稳定剂;
至少一种碱;及
水,
其中所述蚀刻剂组合物不含氨或氢氧化铵且具有7.5到13的pH。
2.根据权利要求1所述的蚀刻剂组合物,其中所述氧化剂包含选自由以下组成的群组的物质:过氧化氢(H2O2)、FeCl3、FeF3、Fe(NO3)3、Sr(NO3)2、CoF3、MnF3、过一硫酸氢钾(oxone)、(2KHSO5·KHSO4·K2SO4)、硝酸(HNO3)、过氧单硫酸氢铵、亚氯酸铵(NH4ClO2)、氯酸铵(NH4ClO3)、碘酸铵(NH4IO3)、硝酸铵(NH4NO3)、过硼酸铵(NH4BO3)、过氯酸铵(NH4ClO4)、过碘酸铵(NH4IO4)、过硫酸铵((NH4)2S2O8)、次氯酸铵(NH4ClO)、钨酸铵((NH4)10H2(W2O7))、过硫酸钠(Na2S2O8)、次氯酸钠(NaClO)、过硼酸钠、碘酸钾(KIO3)、过锰酸钾(KMnO4)、过硫酸钾(K2S2O8)、次氯酸钾(KClO)、四甲基亚氯酸铵((N(CH3)4)ClO2)、四甲基氯酸铵((N(CH3)4)ClO3)、四甲基碘酸铵((N(CH3)4)IO3)、四甲基过硼酸铵((N(CH3)4)BO3)、四甲基过氯酸铵((N(CH3)4)ClO4)、四甲基过碘酸铵((N(CH3)4)IO4)、四甲基过硫酸铵((N(CH3)4)S2O8)、四丁基过氧单硫酸氢铵、过氧单硫酸、过氧化氢脲((CO(NH2)2)H2O2)、过乙酸(CH3(CO)OOH)、叔丁基过氧化氢、硝基苯磺酸盐、1,4-苯醌、甲醌、二甲基-1,4-苯醌、氯醌、四氧嘧啶、过碘酸,及其组合。
3.根据权利要求1所述的蚀刻剂组合物,其中所述至少一种氧化剂包含过氧化氢、脲-过氧化氢、过硫酸铵、过碘酸、过乙酸或叔丁基过氧化氢。
4.根据权利要求1所述的蚀刻剂组合物,其中所述蚀刻剂组合物包含约0.1重量%到约5重量%的所述至少一种氧化剂。
5.根据权利要求1所述的蚀刻剂组合物,其中所述至少一种氧化剂稳定剂包含选自由以下组成的群组的物质:甘氨酸、丝氨酸、脯氨酸、亮氨酸、丙氨酸、天冬酰氨酸、天冬氨酸、谷酰氨酸、缬氨酸及赖氨酸、氮基三乙酸、亚氨基二乙酸、羟乙膦酸、乙二胺四乙酸(EDTA)、(1,2-亚环己基二氮基)四乙酸(CDTA)、尿酸、四乙二醇二甲醚、二乙三胺五乙酸、丙二胺四乙酸、乙二胺二琥珀酸、胺苯磺酰胺,及其组合。
6.根据权利要求5所述的蚀刻剂组合物,其中所述氧化剂稳定剂包含CDTA或EDTA。
7.根据权利要求1所述的蚀刻剂组合物,其中所述蚀刻剂组合物包含约0.0001重量%到约1.0重量%的所述至少一种氧化剂稳定剂。
8.根据权利要求1所述的蚀刻剂组合物,其中所述碱包含选自由以下组成的群组的物质:碱金属氢氧化物、碱土金属氢氧化物、四甲基氢氧化铵(TMAH)、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)、苯甲基三甲基氢氧化铵(BTMAH)、氢氧化胆碱、乙基三甲基氢氧化铵、三(2-羟乙基)甲基氢氧化铵、二乙基二甲基氢氧化铵、四丁基氢氧化磷(TBPH)、四甲基氢氧化磷、四乙基氢氧化磷、四丙基氢氧化磷、苯甲基三苯基氢氧化磷、甲基三苯基氢氧化磷、乙基三苯基氢氧化磷、正丙基三苯基氢氧化磷,及其组合。
9.根据权利要求1所述的蚀刻剂组合物,其中所述碱包含四甲基氢氧化铵、氢氧化胆碱,或其组合。
10.根据权利要求1所述的蚀刻剂组合物,其中所述蚀刻剂组合物包含约0.1重量%到约10重量%的所述碱。
11.根据权利要求1所述的蚀刻剂组合物,其中所述蚀刻剂组合物具有介于8与11之间的pH。
12.根据权利要求1所述的蚀刻剂组合物,其中所述蚀刻剂组合物进一步包含至少一种络合剂。
13.根据权利要求12所述的蚀刻剂组合物,其中所述至少一种络合剂包含选自由以下组成的群组的物质:氨基乙基乙醇胺、N-甲基氨基乙醇、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(MEA)、三乙醇胺(TEA)、1-氨基-2-丙醇、2-氨基-1-丁醇、异丁醇胺、三乙二胺、4-(2-羟乙基)吗啉(HEM)、乙二胺四乙酸(EDTA)、间苯二甲胺(MXDA)、亚氨基二乙酸(IDA)、2-(羟乙基)亚氨基二乙酸(HIDA)、氮基三乙酸、硫脲、1,1,3,3-四甲基脲、脲、脲衍生物、尿酸、丙氨酸、精氨酸、天冬酰氨酸、天冬氨酸、半胱氨酸、谷氨酸、谷酰氨酸、组氨酸、异亮氨酸、亮氨酸、赖氨酸、甲硫氨酸、苯基丙氨酸、脯氨酸、丝氨酸、苏氨酸、色氨酸、酪氨酸、缬氨酸、1-羟基亚乙基-1,1-二膦酸(HEDP)、1,5,9-三氮杂环十二烷-N,N',N"-三(亚甲基膦酸)(DOTRP)、1,4,7,10-四氮杂环十二烷-N,N',N",N'"-四(亚甲基膦酸)(DOTP)、氮基三(亚甲基)三膦酸、二乙三胺五(亚甲基膦酸)(DETAP)、氨基三(亚甲基膦酸)、双(六亚甲基)三胺五亚甲基膦酸、1,4,7-三氮杂环壬烷-N,N',N"-三(亚甲基膦酸(NOTP)、羟乙基二膦酸盐、氮基三(亚甲基)膦酸、2-膦酰基-丁烷-1,2,3,4-四羧酸、羧乙基膦酸、氨基乙基膦酸、草甘膦、乙二胺四(亚甲基膦酸)苯基膦酸、草酸、琥珀酸、马来酸、苹果酸、丙二酸、己二酸、邻苯二甲酸、柠檬酸、柠檬酸钠、柠檬酸钾、柠檬酸铵、丙三羧酸、三羟甲基丙酸、酒石酸、葡萄糖醛酸、2-羧基吡啶、4,5-二羟基-1,3-苯二磺酸二钠盐,及其组合。
14.根据权利要求1所述的蚀刻剂组合物,其中所述蚀刻剂组合物进一步包含至少一种有机溶剂。
15.根据权利要求14所述的蚀刻剂组合物,其中所述至少一种有机溶剂包含选自由以下组成的群组的物质,其中有机添加剂包含选自由以下组成的群组的物质: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、二甲基砜、乙二醇、丙二醇、二丙二醇、四甘醇、二甘醇二甲醚、二甘醇单甲醚、三甘醇单甲醚、二甘醇单乙醚、三甘醇单乙醚、乙二醇单丙醚、乙二醇单丁醚、二甘醇单丁醚(DEGBE)、三甘醇单丁醚(TEGBE)、乙二醇单己醚(EGHE)、二甘醇单己醚(DEGHE)、乙二醇苯醚、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、二丙二醇正丁醚、三丙二醇正丁醚或丙二醇苯醚,及其组合。
16.根据权利要求14所述的蚀刻剂组合物,其中所述至少一种有机溶剂是丙二醇。
17.根据权利要求1所述的蚀刻剂组合物,其中所述蚀刻剂组合物进一步包含至少一种金属腐蚀抑制剂。
18.根据权利要求17所述的蚀刻剂组合物,其中所述至少一种金属腐蚀抑制剂包含选自由以下组成的群组的物质:5-氨基四唑、5-苯基-苯并三唑、1H-四唑-5-乙酸、1-苯基-2-四唑啉-5-硫酮、苯并咪唑、甲基四唑、吡唑、5-氨基-1,3,4-噻二唑-2-硫醇(ATDT)、苯并三唑(BTA)、1,2,4-三唑(TAZ)、1,2,3-三唑、甲苯基三唑、5-甲基-苯并三唑(mBTA)、5-苯基-苯并三唑、5-硝基-苯并三唑、苯并三唑羧酸、3-氨基-5-巯基-1,2,4-三唑、1-氨基-1,2,4-三唑、羟基苯并三唑、2-(5-氨基-戊基)-苯并三唑、1-氨基-1,2,3-三唑、1-氨基-5-甲基-1,2,3-三唑、3-氨基-1,2,4-三唑(3-ATA)、3-巯基-1,2,4-三唑、3-异丙基-1,2,4-三唑、5-苯基硫醇-苯并三唑、卤基-苯并三唑(卤基=F、Cl、Br或I)、萘三唑、2-巯基苯并咪唑(MBI)、2-巯基苯并噻唑、4-甲基-2-苯基咪唑、2-巯基噻唑啉、5-氨基-1,2,4-三唑(5-ATA)、3-氨基-5-巯基-1,2,4-三唑、戊四唑、5-苯基-1H-四唑、5-苯甲基-1H-四唑、2,4-二氨基-6-甲基-1,3,5-三嗪、噻唑、三嗪、甲基四唑、1,3-二甲基-2-咪唑烷酮、1,5-五亚甲基四唑、1-苯基-5-巯基四唑、二氨基甲基三嗪、咪唑啉硫酮、4-甲基-4H-1,2,4-三唑-3-硫醇、4-氨基-4H-1,2,4-三唑、3-氨基-5-甲基硫基-1H-1,2,4-三唑、苯并噻唑、咪唑、吲唑、腺嘌呤、腺苷、咔唑,及其组合。
19.根据权利要求18所述的蚀刻剂组合物,其中所述至少一种金属腐蚀抑制剂是甲苯基三唑。
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