CN1325591C - 用于cmp的经正电性聚电解质处理的阴离子性研磨颗粒 - Google Patents
用于cmp的经正电性聚电解质处理的阴离子性研磨颗粒 Download PDFInfo
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- CN1325591C CN1325591C CNB03803719XA CN03803719A CN1325591C CN 1325591 C CN1325591 C CN 1325591C CN B03803719X A CNB03803719X A CN B03803719XA CN 03803719 A CN03803719 A CN 03803719A CN 1325591 C CN1325591 C CN 1325591C
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- 150000002500 ions Chemical class 0.000 description 1
- MVFCKEFYUDZOCX-UHFFFAOYSA-N iron(2+);dinitrate Chemical compound [Fe+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MVFCKEFYUDZOCX-UHFFFAOYSA-N 0.000 description 1
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- 239000007800 oxidant agent Substances 0.000 description 1
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 description 1
- LLYCMZGLHLKPPU-UHFFFAOYSA-N perbromic acid Chemical compound OBr(=O)(=O)=O LLYCMZGLHLKPPU-UHFFFAOYSA-N 0.000 description 1
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- KMUONIBRACKNSN-UHFFFAOYSA-N potassium dichromate Chemical compound [K+].[K+].[O-][Cr](=O)(=O)O[Cr]([O-])(=O)=O KMUONIBRACKNSN-UHFFFAOYSA-N 0.000 description 1
- IWZKICVEHNUQTL-UHFFFAOYSA-M potassium hydrogen phthalate Chemical compound [K+].OC(=O)C1=CC=CC=C1C([O-])=O IWZKICVEHNUQTL-UHFFFAOYSA-M 0.000 description 1
- 229940079877 pyrogallol Drugs 0.000 description 1
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- PFUVRDFDKPNGAV-UHFFFAOYSA-N sodium peroxide Chemical compound [Na+].[Na+].[O-][O-] PFUVRDFDKPNGAV-UHFFFAOYSA-N 0.000 description 1
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- ISIJQEHRDSCQIU-UHFFFAOYSA-N tert-butyl 2,7-diazaspiro[4.5]decane-7-carboxylate Chemical compound C1N(C(=O)OC(C)(C)C)CCCC11CNCC1 ISIJQEHRDSCQIU-UHFFFAOYSA-N 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
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- WBYWAXJHAXSJNI-VOTSOKGWSA-M trans-cinnamate Chemical compound [O-]C(=O)\C=C\C1=CC=CC=C1 WBYWAXJHAXSJNI-VOTSOKGWSA-M 0.000 description 1
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- BYGOPQKDHGXNCD-UHFFFAOYSA-N tripotassium;iron(3+);hexacyanide Chemical compound [K+].[K+].[K+].[Fe+3].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-] BYGOPQKDHGXNCD-UHFFFAOYSA-N 0.000 description 1
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K3/00—Materials not provided for elsewhere
- C09K3/14—Anti-slip materials; Abrasives
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K3/00—Materials not provided for elsewhere
- C09K3/14—Anti-slip materials; Abrasives
- C09K3/1454—Abrasive powders, suspensions and pastes for polishing
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B24—GRINDING; POLISHING
- B24B—MACHINES, DEVICES, OR PROCESSES FOR GRINDING OR POLISHING; DRESSING OR CONDITIONING OF ABRADING SURFACES; FEEDING OF GRINDING, POLISHING, OR LAPPING AGENTS
- B24B37/00—Lapping machines or devices; Accessories
- B24B37/04—Lapping machines or devices; Accessories designed for working plane surfaces
- B24B37/042—Lapping machines or devices; Accessories designed for working plane surfaces operating processes therefor
- B24B37/044—Lapping machines or devices; Accessories designed for working plane surfaces operating processes therefor characterised by the composition of the lapping agent
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B24—GRINDING; POLISHING
- B24B—MACHINES, DEVICES, OR PROCESSES FOR GRINDING OR POLISHING; DRESSING OR CONDITIONING OF ABRADING SURFACES; FEEDING OF GRINDING, POLISHING, OR LAPPING AGENTS
- B24B37/00—Lapping machines or devices; Accessories
- B24B37/04—Lapping machines or devices; Accessories designed for working plane surfaces
- B24B37/046—Lapping machines or devices; Accessories designed for working plane surfaces using electric current
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09G—POLISHING COMPOSITIONS; SKI WAXES
- C09G1/00—Polishing compositions
- C09G1/02—Polishing compositions containing abrasives or grinding agents
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K3/00—Materials not provided for elsewhere
- C09K3/14—Anti-slip materials; Abrasives
- C09K3/1436—Composite particles, e.g. coated particles
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Composite Materials (AREA)
- Mechanical Treatment Of Semiconductor (AREA)
- Finish Polishing, Edge Sharpening, And Grinding By Specific Grinding Devices (AREA)
- Disintegrating Or Milling (AREA)
Abstract
本发明提供化学机械抛光体系及利用该抛光体系抛光基底的方法,其中该体系包括(a)研磨剂,(b)液体载剂,及(c)分子量为约15,000或更高的正电性聚电解质,其中该研磨剂包括与该正电性聚电解质静电结合的颗粒。
Description
技术领域
本发明关于包含覆有聚电解质的研磨剂的抛光组合物,以及其在化学机械抛光(CMP)中的使用方法。
背景技术
平面化或抛光基底表面的结合物及方法在本领域里众所周知。抛光组合物(亦知为的抛光浆)典型地在水溶液中含有研磨物质、并可通过表面与被该抛光组合物饱和的抛光垫接触而应用在该表面上。典型的研磨物质包括二氧化硅、氧化铈、氧化铝、氧化锆及氧化锡。例如,美国专利第5,527,423号描述一种通过表面与抛光浆接触以化学机械抛光金属层的方法,其中该抛光浆是在水溶性媒介中含有高纯度的细金属氧化物颗粒。或者,将研磨物质掺入抛光垫中。美国专利第5,489,233号公开具有表面网纹或图案的抛光垫的用途,而美国专利第5,958,794号公开一种固定的研磨抛光垫。
常用的抛光体系及抛光方法典型地在平面化半导体晶片方面不完全令人满意。具体而言,抛光组合物及抛光垫的抛光速率不尽理想,而且用于化学机械抛光半导体表面时所获得的表面质量不佳。因为半导体晶片的性能是与其表面的平面性有直接关系,因此使用一种高质量抛光的抛光组合物及方法是重要的,该方法可获得高抛光效率、均匀度及去除率并留下最少表面缺陷。
创造用于半导体晶片的有效抛光体系的困难源自于半导体晶片的复杂性。半导体晶片典型地由其上已形成多个晶体管的基底所构成。集成电路通过图案化基底中的区域及基底上的各层以化学及物理方式连接基底。为制造可操作的半导体晶片并最大化晶片产量、性能及可靠性,希望能抛光所选晶片表面,而对下面结构或形貌无不利影响。事实上,如果过程步骤不是在经足够平面化的晶片表面上完成,则半导体制造时可能发生许多问题。
聚电解质在化学机械抛光组合物中的使用是在本领域中普遍已知。在某些情形中,聚电解质是用作去除表面层的配合剂;在其它情形中,聚电解质作为分散剂、增稠剂或絮凝剂添加以改良抛光组合物的性质;而且在其它情形中,聚电解质是用于改良研磨颗粒表面。
下列专利及专利申请是公开含有聚电解质的抛光组合物,其中该聚电解质据称可配合基底表面。美国专利第6,099,604号公开一种抛光组合物,其包含溶剂、研磨颗粒及聚羧酸螯合剂,该螯合剂据称可稳定被化学机械抛光程序移出的基底部分。WO99/64527公开一种抛光组合物,其包含水、研磨剂、氧化剂、任选的配合剂和/或分散剂和有机聚合物以柔和地去除氧化物膜。WO01/14496公开一种抛光组合物,其包含主链含至少16个碳的有机聚合物及任选的研磨颗粒、防止研磨颗粒团聚的分散剂、氧化剂和配合剂。有机聚合物被设计成黏在已抛光晶片表面,因此可消除残留物的刮伤及再沉积。美国专利第6,117,775号公开一种抛光组合物,其包含低于1重量%的研磨颗粒、氧化剂、有机酸及据称可抑制蚀刻及氧化作用的表面活性剂。美国专利第6,303,049号公开一种抛光组合物,其包含研磨剂、增磨剂(亚磷酸)及水溶性阴离子性化学药品(如含丙烯酸盐、磷酸盐、硫酸盐的化合物、聚合物和/或共聚物),该阴离子性化学药品据称在抛光期间可覆盖在金属膜表面上。
下列专利及专利申请是公开含有聚电解质的抛光组合物,其中该聚电解质据称可用于改良抛光组合物的性质。美国专利第4,752,628号公开一种抛光组合物,其由精细分开的无机研磨剂、杀虫剂、羧酸分散剂聚合物、羧酸聚合物增稠剂、腐蚀抑制剂及任选的润滑剂组成。美国专利第4,867,757号公开一种pH大于8.5的抛光组合物,其是由精细分开的无机研磨剂、羧酸分散剂聚合物及润滑剂组成的。美国专利第5,123,958号公开一种抛光组合物,其包含研磨剂、含有聚乙烯基醇及水的混合物的凝胶型载剂和任选的聚电解质絮凝剂。美国专利第5,352,277号公开一种抛光组合物,其包含水、胶状二氧化硅、水溶性聚合体化合物及碱性pH的水溶性盐,该聚合体化合物据称可帮助抛光期间在抛光垫与基底表面之间形成规则层流。美国专利第5,860,848号公开一种抛光组合物,其包含水、次微米二氧化硅颗粒、盐、胺化合物及pH8-11的聚电解质,该聚电解质据称可降低颗粒对基底表面的黏性。美国专利第6,117,220号公开一种抛光组合物,其包含水、聚苯乙烯磺酸、无机或有机酸及研磨剂,该聚苯乙烯磺酸据称可用于絮凝化研磨颗粒,产生一种在化学机械抛光期间具有良好防沫性质及低表面腐蚀发生率的抛光组合物。美国专利第6,117,783号公开一种抛光组合物,其包含羟基胺化合物及足够的聚电解质以驱离颗粒隔开彼此与基底表面。美国专利第6,132,637号公开一种抛光组合物,其包含水溶性媒介、研磨剂、表面活性剂、有机聚合物及配合剂,其中该配合物具有两个或多个可配合二氧化硅及氮化硅的酸基。该有机聚合物据称可用于提高抛光组合物的黏度并抑制将以该抛光组合物进行抛光的基底刮伤。美国专利第6,171,352号公开一种抛光组合物,其包含水溶性媒介、研磨剂、研磨加速剂及任选的可降低抛光组合物黏度的硝酸盐或阴离子性表面活性剂(如聚羧酸)。JP1087146公开一种抛光组合物,它含有研磨剂及聚苯乙烯磺酸,其据称是用作分散剂并改善抛光效果。
下列专利及专利申请是公开含有研磨颗粒的抛光组合物,其中该研磨颗粒据称可与聚电解质以静电方式相互作用。美国专利第5,876,490号公开一种抛光组合物,其包含研磨颗粒及电荷不同于研磨颗粒的聚电解质(分子量为500至10,000),该聚电解质据称可覆盖在研磨颗粒表面上,导致改善的抛光行为。EP1036836A1公开一种抛光组合物,其包含一种热塑性树脂的聚合物颗粒与无机颗粒的水溶性分散液,其中该无机颗粒具有相反泽塔(ζ)电位并且是以静电力结合。同样地,EP1104778A2公开一种含有复合颗粒的抛光组合物,其中该复合颗粒是由无机颗粒与相反泽塔(ζ)电位的聚合物颗粒组成的。EP1118647A1公开一种抛光组合物,其包含研磨剂、氧化剂、共氧化剂及抗凝结剂,该抗凝结剂据称可用于稳定胶体颗粒,对抗凝结剂的分子量范围无任何描述。JP200164631公开一种抛光组合物,其包含研磨剂及含有磺酸基的聚合物或共聚物(MW为5,000至20,000),该聚合物据称可黏在化学机械抛光期间所产生的抛光废弃物上。WO01/02134公开一种包含水溶性媒介及研磨颗粒的抛光组合物,其中该研磨颗粒是通过离子性物种(如聚电解质及表面活性剂)的存在保留在亚稳定相中,而该离子性物种是覆盖研磨颗粒表面。
然而,仍然需要抛光体系及抛光方法,它们会呈现理想的平面化效率、均匀度及在抛光和平面化基底期间的去除速率,同时最小化缺陷,诸如表面瑕疵及在抛光和平面化期间对下面结构及形貌的危害。
本发明寻求提供此种化学机械抛光体系及方法,由在此所提供的本发明描述可清楚了解本发明这些及其它优点。
发明内容
本发明提供化学机械抛光(chemical-mechanical polishing)(“CMP”)体系,其包含(a)研磨剂,(b)液体载剂,及(c)分子量为15,000或更高的正电性聚电解质,其中该研磨剂包含与正电性聚电解质静电结合的颗粒。本发明还提供利用该化学机械抛光体系抛光基底的方法。
本发明关于化学机械抛光(“CMP”)体系,其包含研磨剂、液体载剂及正电性聚电解质。该正电性聚电解质的分子量为15,000或更高,该研磨剂包含与正电性聚电解质静电结合的颗粒。
该CMP体系典型地进一步包括抛光垫。研磨颗粒可为任何适合颗粒并可固定在抛光垫上和/或可呈微粒形态并悬浮于液体载剂中。抛光垫可为任何适合的抛光垫。研磨剂(当存在并悬浮在液体载剂中时)与正电性聚电解质以及任何悬浮于液体载剂的其它组份形成CMP体系的抛光组合物。
该正电性聚电解质与研磨颗粒是以静电方式结合使至少一部分颗粒表面被聚电解质所覆盖,该聚电解质是呈正电性并与任何在CMP体系的pH下具有适合泽塔(ζ)电位的研磨颗粒结合。研磨颗粒的泽塔(ζ)电位相当于研磨颗粒周围的离子与整个溶液(如液体载剂及任何溶于其中的其它组份)间的电荷差。研磨颗粒的泽塔(ζ)电位将随pH而变,研磨颗粒在CMP体系的pH下最好具有负泽塔(ζ)电位。在某些情形中,具有负泽塔电位的研磨颗粒可在具有正泽塔(ζ)电位的研磨颗粒暴露于正电性聚电解质中之前,以电荷反转剂处理的而获得。该电荷反转剂典型地为无机酸、有机酸或其盐,例如,该电荷反转剂可为酒石酸。
该研磨颗粒可为任何适合研磨颗粒,例如该研磨颗粒可为天然或合成的并可包含钻石(如多晶钻石)、石榴石、玻璃、金刚砂、金属氧化物、碳化物、氮化物及类似物。典型地,研磨颗粒选自二氧化硅、氧化铝、二氧化钛、氧化锆、三氧化二铈、氧化锗、氧化镁、氮化硅、碳化硅、碳化硼、碳化钛、二硼化钛、碳化钨、钻石、其共形成产物及其结合物。优选地,研磨颗粒包含二氧化硅或氧化铝。
正电性聚电解质可为任何适合的正电性聚电解质,而且CMP体系可包含一种或多种此类正电性聚电解质,该正电性聚电解质最好是一种含有正电性官能团的聚合物或表面活性剂。典型地,正电性聚电解质包含基于氮的官能团。例如,聚电解质可为含有一级、二级、三级或四级胺官能团的聚胺或其混合物。聚电解质可为具有亲水溶性(含氮)头基及疏水溶性尾基的阳离子性表面活性剂。聚电解质最好包含一或多个重复单元,其中该重复单元是包含选自胺、酰胺、酰亚胺、亚胺、烷基胺及氨基醇的官能团。聚电解质为只含上述重复单元的聚合物或共聚物,或者为含有这些重复单元中的一或多个结合其它(优选为非离子性)的重复单元,例如环氧乙烷、环氧丙烷、苯乙烯及其混合物的共聚物。非离子性重复单元可存在于正电性聚电解质中以在重复单元间导入空间关系。非离子性重复单元在聚电解质中的存在数目最好不超过重复单元总数的99%(如95%)。优选地,非离子性重复单元在聚电解质中的存在数目不超过90%(如85%)。聚电解质也可是一种含有上述重复单元结合其它重复单元的共聚物,其中该其它重复单元包含的官能团包括,例如醇类、膦酸、膦酸盐(酯)、硫酸盐(酯)、磺酸、磺酸盐(酯)、磷酸盐(酯)、羧酸、羧酸盐(酯)及其混合物等。聚电解质可为均聚物、无规共聚物、交替共聚物、周期共聚物、嵌段共聚物(如AB、ABA、ABC等)、接枝共聚物或梳状共聚物(comb copolymer)。
非离子性或其它含有官能团的重复单元与阳离子性含氮重复单元结合可最优选化CMP的效果。经由重复单元的类型及相对量的变化可改良并最优选化正电性聚电解质与研磨颗粒表面、基底表面、抛光垫表面及液体载剂的相互作用。适合的聚电解质包括聚氮丙啶、聚氨基酰胺、聚(二烯丙基二甲基氯化铵)、聚(二甲基胺-共-表氯醇)、聚(甲基丙烯酰氧基乙基三甲基氯化铵)、聚(甲基丙烯酰氧基乙基二甲基苯甲基氯化铵)、聚(乙烯基吡咯烷酮)、聚(乙烯基咪唑)、聚(乙烯基吡啶)、聚(乙烯基胺)、含有侧链胺基的硅氧烷聚合物或共聚物及其结合物。优选地,正电性聚电解质是聚氮丙啶。
在第一具体实施例中,正电性聚电解质与研磨颗粒的结合是形成胶体稳定的研磨剂。胶体是指研磨颗粒在液体载剂中的悬浮物。胶体稳定性是指随时间保持悬浮状态。在本发明的文中,将研磨剂放入100毫升量筒中并使其未搅拌静置2小时的时间,若量筒底部50毫升的颗粒浓度([B],以克/毫升为单位)与量筒顶部50毫升的颗粒浓度([T],以克/毫升为单位)间的差除以研磨结合物中颗粒的初浓度([C],以克/毫升为单位)是小于或等于0.5(即{[B]-[T]}/[C]≤0.5),则研磨剂被视为是胶体稳定的。第一具体实施例的正电性聚电解质的分子量最好为15,000或更高(如20,000或更高)。典型地,正电性聚电解质的分子量为5,000,000或更低。优选地,正电性聚电解质的分子量为20,000至3,000,000(如35,000至2,000,000或50,000至1,000,000)。预期较高分子量聚电解质(如15,000或更高)可提供研磨颗粒周围比较低分子量(如10,000或更低)聚电解质更厚的立体屏壁。在非常高的分子量(如MW为3,000,000或更高,如2,000,000或更高)下,研磨剂的胶体稳定性可能降低。
在第二具体实施例中,正电性聚电解质的分子量最好为15,000或更高(如20,000或更高)和2,000,000或更低。优选地,正电性聚电解质的分子量为20,000至1,500,000(如50,000至1,000,000)。
当研磨剂是存在于CMP体系中并悬浮于液体载剂中时(即当研磨剂为抛光组合物的组份时),任何适合量的研磨剂皆可存在于抛光组合物中。典型地,0.01重量%或更多(如0.05重量%或更多)研磨颗粒将存在于抛光组合物中。更典型地,0.1重量%或更多研磨颗粒将存在于抛光组合物中。抛光组合物中的研磨颗粒量典型地将不超过20重量%,更典型地将不超过10重量%(如将不超过5重量%)。优选地,抛光组合物中的研磨颗粒量为0.05重量%至8重量%,更优选为0.1重量%至5重量%,最优选为0.5重量%至3重量%。
液体载剂用于帮助研磨剂(当存在并悬浮于液体载剂中时)和正电性聚电解质或其盐类以及任何选用添加剂,应用在将要抛光或平面化的适合基底表面上。液体载剂典型地为水溶性载剂并可只为水,可包含水和可与水互溶的适合溶剂,或者为乳液。可与水互溶的适合溶剂包括醇类如甲醇、乙醇等。优选地,水溶性载剂是由水组成,更优选是由去离子水组成。
在此所描述的CMP体系的pH保持在适合其希望最终用途的范围内。CMP体系中所用的pH视几项因素而定,包括(i)聚电解质的pKa(当聚电解质为含氮聚合物或表面活性剂时),(ii)研磨颗粒的泽塔(ζ)电位及(iii)将要抛光基底的类型。含氮聚电解质的阳离子性质为依赖pH的性质。为确保聚电解质充分覆盖(如吸附)在研磨颗粒上,最好调整pH使5%或更多聚电解质的官能团是呈正电性。这是指CMP体系的pH最好比5%或更多聚电解质的官能团的pKa至少低1单位。而且,研磨颗粒在CMP体系的pH下应具有负泽塔(ζ)电位。因此,pH应保持在高于研磨颗粒的等电点(泽塔电位为零的pH)的值。
当CMP体系与抛光含铜基底结合使用时,pH最好为7或更低,优选为3至6,更优选是3.5至5(如pH为4)。当CMP体系是用于抛光含铂基底时,pH最好为2至7。当CMP体系是用于抛光含钌基底时,pH最好为5或更高,优选是7至11。当CMP体系是用于抛光含铱基底时,pH最好为5至12,优选7至9。
CMP体系视情况进一步包括氧化剂,该氧化剂可为任何适合的氧化剂。适合的氧化剂包括无机及有机的过态-化合物(per-compound)、溴酸盐、硝酸盐、氯酸盐、铬酸盐、碘酸盐、铁及铜盐(如硝酸盐、硫酸盐、EDTA及柠檬酸盐)、稀土及过渡金属氧化物(如四氧化锇)、铁氰化钾、重铬酸钾、碘酸及类似物。过态-化合物(如《海氏简明化学词典》(Hawley’s CondensedChemical Dictionary)所定义)为含至少一个过氧基(--O--O--)的化合物、或含在其最高氧化状态的元素的化合物。含有至少一个过氧基的化合物实例包括(但不限于)过氧化氢及其加成物如尿素过氧化氢和过碳酸盐、有机过氧化物如过氧化苯甲酰、过乙酸及二-叔丁基过氧化物、单过硫酸盐(SO5 2-)、二过硫酸盐(S2O8 2-)及过氧化钠。含最高氧化态元素的化合物实例包括(但不限于)高碘酸、高碘酸盐、过溴酸、过溴酸盐、高氯酸、高氯酸盐、过硼酸、过硼酸盐及高锰酸盐。氧化剂最好为过氧化氢。
CMP体系视情况进一步包括腐蚀抑制剂(即成膜剂)。该腐蚀抑制剂可为任何适合的腐蚀抑制剂。典型地,腐蚀抑制剂为含有具杂原子官能团的有机化合物。例如,成膜剂为具有至少一个5或6员杂环作为活性官能团的杂环有机化合物,其中该杂环包含至少一个氮原子,例如唑化合物。优选地,成膜剂为三唑,更优选是1,2,4-三唑、1,2,3-三唑或苯并三唑。
CMP体系视情况进一步包括非离子性表面活性剂。适合的非离子性表面活性剂的实例为Tetronic表面活性剂,可由BASF公司购得。
CMP体系视情况进一步包括螯合或配合剂。该配合剂为任何适合提高将要去除基底层的去除速率的化学添加剂。适合的螯合或配合剂可包括,例如羰基化合物(如乙酰丙酮化物及类似物)、简单羧酸盐(如乙酸盐、芳基羧酸盐及类似物)、含有一个或多个羟基的羧酸盐(如乙醇酸盐、乳酸盐、葡糖酸盐、没食子酸及其盐和类似物)、二-、三-及多-羧酸盐(如草酸盐、苯二甲酸盐、柠檬酸盐、肉桂酸盐、酒石酸盐、苹果酸盐、乙二胺四乙酸盐(如EDTA二钾)、其混合物及类似物)、含有一个或多个磺酸和/或膦酸基的羧酸盐及类似物。适合的螯合或配合剂也包括,例如二-、三-或多元醇(如乙二醇、邻苯二酚、连苯三酚、丹宁酸及类似物)及含胺化合物(如氨、氨基酸、氨基醇、二-、三-及聚胺和类似物)。优选地,配合剂是羧酸盐,更优选是为草酸盐。螯合或配合剂的选择将视将要去除基底层的类型而定。
应了解许多上述化合物可以作为盐(如金属盐、铵盐或类似物)、酸或部分盐的型态存在。例如,柠檬酸盐包括柠檬酸以及其单-、二-和三-盐;苯二甲酸盐包括苯二甲酸以及其单盐(如苯二甲酸氢钾)和二盐;高氯酸盐包括对应酸(如高氯酸)以及其盐类。另外,特定化合物或试剂可完成超过一种功能。例如,部分化合物可作为螯合剂及氧化剂(如特定的硝酸铁及类似物)。
在此所描述的CMP体系可用于抛光(如平面化)基底。抛光基底的方法是包括(i)提供化学机械抛光体系,(ii)将基底与该化学机械抛光体系接触,及(iii)磨掉至少一部分基底以抛光该基底。该化学机械抛光体系最好可用于抛光包含至少一个金属层及任选的绝缘层的基底的方法中,由此使基底与该化学机械抛光体系接触、并磨掉基底中至少一部分金属层或绝缘层(若存在)使金属层或绝缘层被抛光。基底可为任何适合的基底(如集成电路、内存或硬盘、金属、ILD层、半导体、微电机械体系、铁电、磁头、聚合膜及低和高介电常数膜)并可包含任何适合的绝缘、金属或金属合金层(如金属传导层)。绝缘层可为金属氧化物、多孔金属氧化物、玻璃、有机聚合物、氟化有机聚合物或任何其它适合的高或低-k绝缘层。绝缘层最好包含氧化硅、氮化硅、氧氮化硅、碳化硅、氧化铝或介电常数为3.5或更低的物质。金属层最好包含铜、钨、钛、铝、钽、铂、钌(如二氧化钌)、铑、铱(如二氧化铱)、镍、铁或钴。
本发明CMP体系能够以相当高的速率及理想的平面化效率、均匀度、去除速率和抛光基底时所呈现的选择性来抛光(如平面化)基底。具体而言,CMP体系可理想地以较低缺陷抛光基底。包含覆有正电性聚电解质的颗粒的研磨剂可提供(a)较低的颗粒团聚作用,(b)颗粒的机械及化学性质的改变及(c)颗粒的泽塔(ζ)电位的改变,其可降低将要抛光基底上表面缺陷的数目。包含覆有正电性聚电解质的颗粒的研磨剂也可在基底层之间提供改善的选择性。例如,相对于未经覆盖的研磨颗粒,覆有含胺聚电解质的研磨颗粒对绝缘层的去除速率较低。
具体实施方式
下列实施例进一步说明本发明,但当然不应以任何方式解释成限制其范围。
实施例1
本实施例说明一种根据本发明呈现胶体稳定性的覆有聚电解质的研磨颗粒的制造方法。
聚(二甲基胺-共-表氯醇-共-乙二胺)溶液(50重量%,MW~75,000)溶于去离子水中,以浓硫酸调整pH,直到在加入二氧化硅后,最终pH为4.5。然后以20,000rpm的速度共混该混合物。在共混期间以6分钟的时间缓慢地将胶状二氧化硅颗粒的悬浮液(50重量%,120纳米,pH4.5的泽塔(ζ)电位为-15至-20毫伏)加入混合物中。另外共混此混合物1分钟,产生含有12重量%二氧化硅及2.5重量%聚电解质的最终组合物。所得覆有聚电解质的二氧化硅颗粒的平均粒径为132纳米。在pH4.5下所测得的泽塔(ζ)电位为+28毫伏。
覆有聚电解质的二氧化硅颗粒与正电性氧化铝颗粒混合(组合物1A,本发明)。类似未经处理的二氧化硅颗粒也与正电性氧化铝颗粒混合(组合物1B,控制组)。混合时,覆有聚电解质的研磨组合物(1A)保持胶体稳定,不像未经处理的研磨组合物(1B)絮凝及沉降。
本实施例证明覆有聚电解质的研磨颗粒可容易地制得及储存以供日后用于化学机械抛光程序中。此实施例也证明覆有聚电解质的颗粒可克服未经处理的研磨剂所遭遇到的稳定性问题。
实施例2
本实施例说明覆有聚电解质的研磨颗粒不会随时间而团聚。
0.625重量%聚氮丙啶溶于pH7的去离子水,用所形成的溶液处理烘制的(fumed)二氧化硅分散物(5重量%,pH7的泽塔电位为-20毫伏,156纳米)。对该混合物施加高切变约20分钟,产生一种在pH7下泽塔(ζ)电位为+15毫伏的胶体稳定组合物。所得研磨组合物的平均粒径为158纳米。27天后,平均粒径为167纳米。
本实施例证明覆有正电性聚电解质的研磨颗粒是高度稳定的。
实施例3
本实施例证明具有正泽塔(ζ)电位的研磨颗粒可在与电荷反转剂接触时转换电荷,并被正电性聚电解质覆盖以产生稳定的覆有聚电解质的研磨颗粒分散物。
烘制的(fumed)氧化铝分散液(3重量%,pH6的泽塔(ζ)电位=+30至+40毫伏)与酒石酸(1.25重量%)混合。所得研磨颗粒分散液在pH7时的泽塔(ζ)电位为-15毫伏,因此证明具有正泽塔(ζ)电位的研磨剂可通过该研磨剂与电荷反转剂接触而转换电荷。
同样地,用含有酒石酸(100ppm)及聚氮丙啶(0.125重量%)的水溶液处理另一种相同类型的烘制的氧化铝分散液(3重量%,pH6的泽塔(ζ)电位=+30至+40毫伏)并施加高切变20分钟。所得覆有聚氮丙啶的氧化铝颗粒分散液的稳定性超过4个月。
本实施例证明具有正泽塔(ζ)电位的研磨颗粒可用于本发明中,其条件为该研磨颗粒经电荷反转剂的处理。此类研磨颗粒可被正电性聚电解质覆盖并表现出随时间对絮凝作用及沉降的良好抵抗力。
Claims (28)
1.一种化学机械抛光体系,其包括:
(a)研磨剂;
(b)液体载剂;及
(c)正电性聚电解质,其分子量为15,000或更高;
其中该研磨剂是胶体稳定的,并且包括与该正电性聚电解质静电结合的颗粒,至少一部分该颗粒表面被正电性聚电解质所覆盖,该正电性聚电解质为含有正电性官能团的聚合物或表面活性剂。
2.权利要求1的化学机械抛光体系,其中该研磨剂的泽塔电位比与该正电性聚电解质静电结合的颗粒的泽塔电位更加为正。
3.权利要求2的化学机械抛光体系,其中与该正电性聚电解质静电结合的颗粒的泽塔电位是负的。
4.权利要求3的化学机械抛光体系,其中具有负泽塔电位并与该正电性聚电解质静电结合的颗粒,是通过电荷反转剂处理具有正泽塔电位的颗粒获得。
5.权利要求4的化学机械抛光体系,其中该电荷反转剂为无机酸、有机酸或其盐。
6.权利要求1的化学机械抛光体系,其中研磨剂包括颗粒,该颗粒选自氧化硅、氧化铝、二氧化钛、氧化锆、二氧化铈、氧化锗、氧化镁、氮化硅、碳化硅、碳化硼、碳化钛、二硼化钛、碳化钨、钻石、其共形成产物及其组合。
7.权利要求6的化学机械抛光体系,其中该颗粒为氧化硅或氧化铝。
8.权利要求1的化学机械抛光体系,其中该正电性聚电解质的分子量为5,000,000或更低。
9.权利要求1的化学机械抛光体系,其中该正电性聚电解质进一步包括包含官能团的重复单元,该官能团选自醇类、膦酸、膦酸盐、硫酸盐、磺酸、磺酸盐、磷酸盐、羧酸、羧酸盐及其混合物。
10.权利要求1的化学机械抛光体系,其中该正电性聚电解质进一步包括重复单元,该重复单元选自环氧乙烷、环氧丙烷、乙酸乙烯酯及其混合物。
11.权利要求1的化学机械抛光体系,其中该正电性聚电解质为含有一或多个重复单元的聚合物或表面活性剂,其中该重复单元包括官能团,该官能团选自胺、酰胺、酰亚胺、亚胺、烷基胺、氨基醇及其混合物。
12.权利要求11的化学机械抛光体系,其中该正电性聚电解质选自聚氮丙啶、聚氨基酰胺、聚(二烯丙基二甲基氯化铵)、聚(二甲基胺-共-表氯醇)、聚(甲基丙烯酰氧基乙基三甲基氯化铵)、聚(甲基丙烯酰氧基乙基二甲基苯甲基氯化铵)、聚(乙烯基吡咯烷酮)、聚(乙烯基咪唑)、聚(乙烯基吡啶)、聚(乙烯基胺)及其组合。
13.权利要求11的化学机械抛光体系,其中该正电性聚电解质为含有侧链胺基的硅氧烷聚合物或共聚物。
14.权利要求1的化学机械抛光体系,其中正电性聚电解质的全部官能团的5%或更多呈正电性。
15.权利要求1的化学机械抛光体系,其中该体系进一步包括一种或多种组分,该组分选自氧化剂、配合剂及腐蚀抑制剂。
16.权利要求1的化学机械抛光体系,其中该体系进一步包括抛光垫。
17.一种抛光基底的方法,其包括将基底与权利要求1的化学机械抛光体系接触,并磨掉至少一部分基底以抛光该基底。
18.权利要求17的方法,其中该基底包括金属层和/或绝缘层。
19.权利要求18的方法,其中该金属层包括铜、钨、钛、铝、钽、铂、钌、铑、铱、镍、铁或钴。
20.权利要求18的方法,其中该绝缘层包括氧化硅、氮化硅、氧氮化硅、碳化硅、氧化铝或介电常数为3.5或更低的物质。
21.一种化学机械抛光体系,其包括:
(a)研磨剂;
(b)液体载剂;及
(c)正电性聚电解质,其分子量为15,000或以上和2,000,000或以下,其中该正电性聚电解质为含有正电性官能团的聚合物或表面活性剂,并且其中该正电性聚电解质(i)进一步包括包含官能团的重复单元,该官能团选自膦酸、膦酸盐、硫酸盐、磺酸、磺酸盐、磷酸盐、羧酸、羧酸盐及其混合物,(ii)进一步包括重复单元,该重复单元选自环氧乙烷、环氧丙烷、乙酸乙烯酯及其混合物,(iii)含有一个或多个重复单元,该重复单元包含选自酰胺、酰亚胺及其混合物的官能团,或(iv)是含有侧链胺基的硅氧烷聚合物或共聚物;其中该研磨剂包括与该正电性聚电解质静电结合的颗粒。
22.权利要求21的化学机械抛光体系,其中该研磨剂的泽塔电位比与该正电性聚电解质静电结合的颗粒的泽塔电位更加为正。
23.权利要求21的化学机械抛光体系,其中与该正电性聚电解质静电结合的颗粒具有负泽塔电位,是通过电荷反转剂处理具有正泽塔电位的颗粒而获得。
24.权利要求21的化学机械抛光体系,其中该颗粒为氧化硅或氧化铝。
25.权利要求21的化学机械抛光体系,其中正电性聚电解质的所有官能团的5%或更多呈正电性。
26.一种抛光基底的方法,其包括将基底与权利要求21的化学机械抛光体系接触并磨掉至少一部分基底以抛光该基底。
27.权利要求26的方法,其中该基底包括金属层,该金属层包括铜、钨、钛、铝、钽、铂、钌、铑、铱、镍、铁或钴。
28.权利要求26的方法,其中该基底包括绝缘层,该绝缘层包括氧化硅、氮化硅、氧氮化硅、碳化硅、氧化铝或介电常数为3.5或更低的物质。
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Also Published As
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EP1483349B1 (en) | 2007-12-26 |
WO2003068883A1 (en) | 2003-08-21 |
US6776810B1 (en) | 2004-08-17 |
DE60318301D1 (de) | 2008-02-07 |
TWI241339B (en) | 2005-10-11 |
JP4750362B2 (ja) | 2011-08-17 |
US7306637B2 (en) | 2007-12-11 |
KR20100084197A (ko) | 2010-07-23 |
US20040229552A1 (en) | 2004-11-18 |
ATE382076T1 (de) | 2008-01-15 |
EP1483349A1 (en) | 2004-12-08 |
DE60318301T2 (de) | 2008-04-10 |
JP2005518091A (ja) | 2005-06-16 |
AU2003216217A1 (en) | 2003-09-04 |
KR20040088070A (ko) | 2004-10-15 |
TW200302865A (en) | 2003-08-16 |
CN1630697A (zh) | 2005-06-22 |
KR100972730B1 (ko) | 2010-07-27 |
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