CN101085901A - 用于铜膜平面化的钝化化学机械抛光组合物 - Google Patents
用于铜膜平面化的钝化化学机械抛光组合物 Download PDFInfo
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- CN101085901A CN101085901A CNA2007101065751A CN200710106575A CN101085901A CN 101085901 A CN101085901 A CN 101085901A CN A2007101065751 A CNA2007101065751 A CN A2007101065751A CN 200710106575 A CN200710106575 A CN 200710106575A CN 101085901 A CN101085901 A CN 101085901A
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- chemical
- mechanical polishing
- polishing compositions
- copper
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- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims abstract description 72
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Images
Classifications
-
- 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
- C23F3/00—Brightening metals by chemical means
- C23F3/04—Heavy metals
- C23F3/06—Heavy metals with acidic solutions
-
- 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
- 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
- C23F11/00—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent
- C23F11/08—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in other liquids
- C23F11/10—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in other liquids using organic inhibitors
- C23F11/14—Nitrogen-containing compounds
- C23F11/141—Amines; Quaternary ammonium compounds
-
- 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
- C23F3/00—Brightening metals by chemical means
-
- 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 at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer or carrier concentration layer
- H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic System 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
- H01L21/32115—Planarisation
- H01L21/3212—Planarisation by chemical mechanical polishing [CMP]
Abstract
本发明公开了一种CMP组合物,其含有,例如,与氧化剂,螯合剂,研磨剂和溶剂组合的5-氨基四唑。这种CMP组合物有利地缺乏BTA,并对抛光半导体基材上铜元件的表面是有用的,而不会在抛光的铜中出现下陷或其他不利的平面化缺陷,甚至在CMP加工过程中,在铜/CMP组合物界面,本体CMP组合物有显著水平的铜离子,例如Cu2+存在下。
Description
本申请为国际申请PCT/US2003/038047于2005年7月8日进入中国国家阶段、申请号为200380108506.4、发明名称为“用于铜膜平面化的钝化化学机械抛光组合物”的分案申请。
发明领域
本发明涉及化学机械抛光组合物,以及涉及利用该组合物对其上具有铜的半导体基材,例如,铜互连(interconnect),电极,或镀金属,作为晶片基材上的部分半导体装置结构,进行抛光的方法。相关技术描述
铜广泛用于半导体制作中作为晶片基材上半导体装置结构组件的构建材料(例如,接点,电极,导电转接(conductive vias),场发射器基极层等),并且由于其相对于铝及其合金,具有更高的导电性和增加的电迁移阻抗,快速变成在半导体制作中选择的互连金属。
通常,在半导体制作中利用铜的工艺方案包括波形花纹步骤,其中特征被蚀刻在介电物质中。在双波形花纹工艺中,单步用于形成插销和端线。由于铜具有扩散至介电材料的倾向,导致金属端线之间的渗透,所以屏障层,诸如由多种不同的沉积方法沉积的Ta或TaN,经常用于密封铜互连。在沉积屏障层材料之后,铜的薄种子层经由物理蒸汽沉积沉积在屏障材料上,接着电沉积铜以填充部件。然后,沉积的铜可被平面化以赋予其合适的形式,从而在制作半导体成品中适应随后的加工步骤,以及为了令人满意地在存在沉积的铜的微电路中操作。平面化通常包括利用为此目的配制的CMP组合物进行化学机械抛光(CMP)。
由于铜与(Ta或TaN)屏障层间化学反应性中的差异,两种化学截然不同的浆液通常用于铜CMP工艺中。第一步浆液(步骤I)用于快速使形貌(topography)平面化,并且均匀地去除剩余铜,抛光在屏障层上中止。第二步浆液(步骤II)以高去除速率去除屏障层材料,并且在介电氧化物层上停止,或在已涂敷以保护氧化物的帽层上停止。
步骤I平面化及铜的抛光用的化学机械抛光(CMP)组合物通常采用含有一种或多种溶剂,例如水,有机溶剂等的溶剂介质的浆液形式,所述浆液含有合适类型研磨剂,例如,选自硅石,氧化铝,以及其他氧化物和矿物材料的研磨剂。
一种类型的使铜表面平面化的CMP组合物包括研磨剂颗粒的水性浆液,含有过氧化氢作为氧化组分和甘氨酸作为螯合剂。已发现甘氨酸与Cu金属氧化形成的Cu+2离子溶液相反应,以形成Cu2+-甘氨酸络合物。通过形成水溶性Cu2+-甘氨酸螯合物使Cu+2离子络合有助于经由直接溶解机制而去除突出区域中的Cu,以及Cu2+-甘氨酸络合物分解过氧化氢从而生成比过氧化氢本身氧化潜力更高的羟基自由基。
FW:119.13)与铜络合,在铜表面上形成不溶性Cu-BTA络合物。所得不溶性保护性膜利于在制装置结构的形貌的平面化,这是因为晶片表面上的凹陷区被免于溶解,同时研磨剂在突出区上的机械作用能够实施材料去除和抛光。此外,Cu-BTA络合物使腐蚀最小化,并且为目的用途保存铜装置结构的功能完整性。
在缺乏由Cu2+-甘氨酸诱导的催化性分解过氧化氢生成的OH基的情况下,BTA作为铜腐蚀抑制剂作用良好。然而,在第一步含有过氧化氢和甘氨酸的铜CMP浆液中,由于铜金属容易在这样的CMP环境中氧化,在动态CMP条件下形成高度氧化OH基不可避免。
向H2O2/甘氨酸/BTA系统中加入Cu2+的试验已显示,Cu2+的存在显著增加Cu的静态蚀刻速率,同时,Cu腐蚀能力转变成较不易腐蚀的范围内。
该发现的意义在于,BTA在CMP加工过程中,不能有效在保护铜晶片表面的低部件,因此当Cu2+阳离子存在于CMP组合物中时,允许“凹陷”发生在高密度的压花区中。
由此,在CMP组合物中,使用BTA作为腐蚀抑制剂的替代品是高度理想的。具体而言,替代的腐蚀抑制剂是期望的,其与基于H2O2/甘氨酸的CMP组合物相容,并且当在CMP加工过程中有显著量的Cu离子存在于本体溶液和/或靠近金属/溶液界面时,能有效钝化铜表面。
发明概述
一方面,本发明涉及用于铜膜平面化的CMP组合物,其中所述组合物包括氧化剂,螯合剂,以及腐蚀抑制剂,并且腐蚀抑制剂包括5-氨基四唑。
在进一步方面,本发明涉及用于铜膜平面化的CMP组合物。所述组合物包括含有研磨剂,溶剂,ATA,H2O2和甘氨酸的水性浆液介质。在所述组合物中,ATA,H2O2和甘氨酸的重量浓度基于组合物的总重如下:
ATA0.01-10wt.%
H2O21-30wt.%
甘氨酸0.1-25wt.%。
本发明的另一方面涉及一种CMP组合物,其以重量百分比基于组合物总重包括下列组分:
ATA0.01-10wt.%
H2O21-30wt.%
甘氨酸0.1-25wt.%
研磨剂0-30wt.%
水30-90wt.%
所有组分在组合物中的总wt.%共计100wt.%。
本发明的另一方面涉及在其上具有铜的基材上抛光铜的方法,包括在CMP条件下,将基材上的铜与有效抛光铜的CMP组合物接触,其中CMP组合物包括ATA。
本发明的其他方面,特征和实施方案从随后的公开内容和随附的权利要求书中会更显而易见。
附图简述
图1示出铜金属的静态蚀刻速率,以/min表示,作为添加的硫酸铜(CuSO4·5H2O)浓度的函数,在pH 3.5的H2O2/甘氨酸/Cu2+系统中,对(i)5%H2O2和1%甘氨酸,(ii)5%H2O2,1%甘氨酸,和0.15%BTA,(iii)5%H2O2,1%甘氨酸,和0.15%5-氨基四唑一水合物,以及(iv)5%H2O2,1%甘氨酸,和0.15%1-羟基苯并三唑。
图2示出铜金属的去除率,以/min表示,作为基于CMP浆液组合物总重的ATA浓度(wt%)的函数。
发明详述及其优选实施方案
本发明基于下列发现:5-氨基四唑(ATA,
FW:85.06)在铜膜平面化的CMP组合物中替代BTA用作腐蚀抑制剂的效果是预料之外的。ATA与含有过氧化氢作为氧化剂以及甘氨酸作为螯合剂的CMP组合物是相容的。含ATA的CMP组合物对铜表面实现了活性钝化,甚至当显著量的铜离子,例如,Cu2+阳离子,在CMP加工过程中存在于本体溶液和/或金属/溶液界面的情况下。
本发明的含ATA的CMP组合物以其广泛的预期,可采用任何合适的成分配制,包括任何合适的氧化剂,螯合剂,以及腐蚀抑制剂,研磨介质,溶剂介质,以及任选的任何合适的添加剂,佐剂,赋形剂等,诸如稳定剂,酸,碱(如,胺),表面活性剂,缓冲剂等。
广泛实施本发明中所用的氧化剂可以任何合适的类型,包括,例如,硝酸铁,草酸铁铵,柠檬酸铁铵,高锰酸盐(如,高锰酸钾),过氧酸(如,过乙酸),过硼酸盐(如,过硼酸钾),过氧化氢脲,碘酸盐(如,碘酸钾),高氯酸盐(如,高氯酸四甲基铵),过硫酸盐,溴酸盐,苯醌,氯酸盐,亚氯酸盐,次氯酸盐,次碘酸盐,溴氧化盐,过碳酸盐,高碘酸盐,铈盐(如,硫酸高铈铵),铬酸盐化合物和重铬酸盐化合物,氰铜酸盐和氰铁化物盐,铁菲咯啉(ferriphenanthroline),吡啶铁(ferripyridine)和铁铈齐(ferrocinium)。优选的氧化剂包括过乙酸,过氧化氢脲,二-t-丁基过氧化物,苄基过氧化物,过氧化氢和包括两种或多种上述氧化剂的相容混合物。
本发明CMP组合物中的螯合剂可以属于任何合适的类型,包括,例如:甘氨酸,丝氨酸,脯氨酸,亮氨酸,丙氨酸,天冬酰胺,天冬氨酸,谷酰胺,缬氨酸,赖氨酸等,多胺络合物及其盐,包括乙二胺四乙酸,N-羟乙基乙二胺三乙酸,氨三乙酸,亚氨基二乙酸,二乙三胺五乙酸,以及乙醇二氨基乙酸;聚羧酸,包括邻苯二甲酸,草酸,苹果酸,琥珀酸,扁桃酸,和苯六酸;以及包括两种或多种上述化合物的相容混合物。优选的螯合剂包括氨基酸,又以甘氨酸为最优选。
ATA以任何合适的浓度用于本发明的CMP组合物中。ATA在特定配方中的合适浓度基于本文公开内容,可由本领域专业人员凭经验容易确定,从而提供即使在含有高水平的铜阳离子的CMP环境中仍具有合适的铜表面钝化特征的CMP组合物。在本发明一个优选实施方案中,CMP组合物中ATA的量基于CMP组合物的总重为约0.01至约10%重量,优选为约0.05至约5%重量,更优选为约0.10至约1.0%重量,以及最优选为约0.2-0.8%重量,尽管在本发明的广泛范围内,更高或更低的百分比可有益于具体应用。
本发明CMP组合物中的腐蚀抑制剂组分包括ATA,并且在本发明的具体实施方案中,还可包括其他腐蚀抑制剂组分与ATA组合。其他这种腐蚀抑制剂组分属于任何合适的类型,例如包括,咪唑,苯并三唑,苯并咪唑,氨基,亚氨基,羧基,巯基,硝基,烷基,脲和硫脲化合物和衍生物等。优选的抑制剂包括四唑及其衍生物,并且本发明预期提供单独的ATA,或与其他四唑(或其他腐蚀抑制剂)组合作为本发明组合物中的腐蚀抑制剂。
研磨剂可属于任何合适的类型,包括但不限于,金属氧化物,硅氮化物,碳化物等。具体的例子包括合适形式,如细粒,颗粒,粒子或其他分开形式的硅石,氧化铝,碳化硅,氮化硅,氧化铁,二氧化铈,氧化锆,氧化锡,二氧化钛,以及两种或多种上述组分的混合物。或者,研磨剂包括形成自两种或多种材料的复合颗粒,例如,NYACOL氧化铝-包被的胶体硅石(Nyacol Nano Teclmologies,Inc.,Ashland,MA)。氧化铝为优选的无机研磨剂,并可用于勃姆石或过渡δ,θ和γ相氧化铝的形式。有机聚合物颗粒,例如,包括热固性和/或热塑性树脂,可用作研磨剂。广泛实施本发明中有用的树脂包括环氧树脂,聚氨酯橡胶,聚酯,聚酰胺,聚碳酸酯,聚烯烃,聚氯乙烯,聚苯乙烯,聚烯烃和(甲基)丙烯酸树脂。两种或多种有机聚合物颗粒的混合物可用作研磨介质,以及包含无机和有机组分的颗粒。
碱在本发明组合物中可任选用于pH调节。例证性碱以实例方式包括,氢氧化钾,氢氧化铵,以及四甲基氢氧化铵(TMAH),四乙基氢氧化铵,三甲基羟乙基氢氧化铵,甲基三(羟乙基)氢氧化铵,四甲基三(羟乙基)氢氧化铵,四(羟乙基)氢氧化铵,以及苄基三甲基氢氧化铵。
酸在本发明组合物中可任选用于调节pH。所用酸属于任何合适的类型,以实例形式包括,甲酸,乙酸,丙酸,丁酸,戊酸,异戊酸,己酸,庚酸,辛酸,壬酸,乳酸,盐酸,硝酸,磷酸,硫酸,氢氟酸,苹果酸,富马酸,丙二酸,戊二酸,乙醇酸,水杨酸,1,2,3-苯三羧酸,酒石酸,葡糖酸,柠檬酸,邻苯二甲酸,焦儿茶酸(pyrocatechoic acid),焦棓酚羧酸,没食子酸,丹宁酸,以及包括两种或多种上述或其他类型化合物的混合物。
胺存在时,可属于任何合适的类型,以实例方式包括,羟胺,单乙醇胺,二乙醇胺,三乙醇胺,二乙二醇胺,N-羟乙基哌嗪,N-甲基乙醇胺,N,N-二甲基乙醇胺,N-乙基乙醇胺,N,N-二乙基乙醇胺,丙醇胺,N,N-二甲基丙醇胺,N-乙基丙醇胺,N,N-二乙基丙醇胺,4-(2-羟乙基)吗啉,氨基乙基哌嗪,以及包括两种或多种上述或其他胺的混合物。
表面活性剂当任选用于本发明组合物中时,可属于任何合适类型,包括非离子,阴离子,阳离子,以及两性表面活性剂,以及聚电解质,例如,包括:有机酸的盐,烷烃硫酸盐(如,十二烷基硫酸钠);烷烃磺酸盐;取代的胺盐(如,十六烷基匹力定溴化物(cetylpyridium bromide));甜菜碱;聚环氧乙烷;聚乙烯醇;聚乙酸乙烯酯;聚丙烯酸;聚乙烯吡咯烷酮;聚乙烯亚胺;以及无水山梨醇的酯,诸如以商标Tween和Span可商购的那些酯,以及包括两种或多种上述或其他表面活性剂的混合物。
本发明CMP组合物的pH可为对所用的具体抛光操作有效的任何合适的值。在一个实施方案中,CMP组合物的pH为约2至约11,更优选约2至约7.0,以及最优选约3至约6。
本发明CMP组合物中所用的溶剂为单组分溶剂或多组分溶剂,这取决于具体应用。在本发明一个实施方案中,CMP组合物中的溶剂为水。在另一实施方案中,溶剂包括有机溶剂,如,甲醇,乙醇,丙醇,丁醇,乙二醇,丙二醇,甘油等。在另一实施方案中,溶剂包括水-醇溶液。广泛种类的溶剂和特异溶剂介质可用于本发明的一般实施,得到溶剂化/悬浮介质,其中分散有研磨剂以及掺入其他组分,从而提供合适特征,例如浆液形式的组合物,用于施加至CMP部件的台板,以在晶片基材上对铜抛光至所需的水平。
在一个实施方案中,本发明提供对其上具有铜的基材,例如,铜互连,镀金属,装置结构元件等进行化学机械抛光有用的CMP组合物,其中组合物包括过氧化氢,甘氨酸,ATA,研磨剂和溶剂。
在另一实施方案中,本发明CMP组合物为水性浆液组合物,并且包括水性介质,研磨剂,ATA,H2O2和甘氨酸,其中ATA,H2O2和甘氨酸的重量组成基于组合物的总重如下:
ATA0.01-10wt.%
H2O21-30wt.%
甘氨酸0.1-25wt.%。
在进一步具体的例证性实施方案中,CMP组合物以重量百分比基于组合物的总重包括下列组分:
ATA0.01-10wt.%
H2O21-30wt.%
甘氨酸0.1-25wt.%
研磨剂0-30wt.%
水30-90wt.%
所有组分在组合物中的总wt.%共计100wt.%。
本发明的CMP组合物容易地配制在所谓的“常用罐”或“储罐”中,或者CMP组合物可以使用时混合的两部分配方或多部分配方的形式提供。多部分配方相对于单一包装的配方的优势在于其延长的保质期。由于在单个包装CMP组合物中存在氧化剂,单个包装配方与多部分配方相比更易分解,从而其属性随时间发生变化。多部分配方的个别部分可在抛光台,抛光带等,或在合适容器中到达抛光台前不久加以混合。
在一个实施方案中,CMP组合物的单个成分各自单独地递送至抛光台,以在台上与配方的其他成分组合而构成CMP组合物备用。在另一实施方案中,CMP组合物配制成两部分,其中第一部分包括研磨剂和腐蚀抑制剂的水性介质,而第二部分包括氧化剂和螯合剂。在另一实施方案中,CMP组合物配制成两部分,其中第一部分包括除氧化剂外的所有组合物的组分,而第二部分包括氧化剂。在所有这些不同的实施方案中,成分或部分混合成最终组合物在使用时才发生,在抛光台,抛光带等,或在合适容器中到达抛光台前不久加以混合。
本发明的铜CMP组合物通过施加CMP组合物至晶片基材上的铜表面而以常规方式用于CMP操作中,以及利用常规抛光元件,诸如抛光垫,抛光带等对铜表面实施抛光。
本发明的CMP组合物有利地用于对半导体基材上的铜元件表面抛光,但在抛光的铜上不会出现凹陷或其他不利的平面化缺陷,甚至当显著量的铜离子,例如,Cu2+阳离子,在CMP加工过程中存在于本体CMP浆液组合物和/或铜/CMP浆液界面的情况下。
本发明的CMP浆液组合物对半导体晶片基材上的铜进行抛光,例如,对压花铜晶片进行抛光是高度有效的。本发明CMP组合物的制备方法是简单地以所需单个包装或多部分配方的方式混合成分,与本文对单个包装和多部分配方的上述讨论一致。各成分的浓度在实施本发明时随具体的CMP组合物配方而广泛变化,并且应理解的是,本发明CMP组合物不同和替代地包括,与本文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。
本发明的特征和优势由下文所述的经验例和结果更充分显示。
实施例1
在CMP浆液组合物的比较测试中,Cu腐蚀速率由电化学方法确定,并且以Cu2+浓度的函数示于图1,其中对多种不同的腐蚀抑制剂进行了测试。更具体而言,图1示出铜金属的静态蚀刻速率,以/min表示,作为添加的硫酸铜(CuSO4·5H2O)浓度的函数,在pH 3.5的H2O2/甘氨酸/Cu2+系统中,采用含有下列成分的各自配方:配方(i)5%H2O2和1%甘氨酸,配方(ii)5%H2O2,1%甘氨酸,和0.15%BTA,配方(iii)5%H2O2,1%甘氨酸,和0.15%5-氨基四唑一水合物,以及配方(iv)5%H2O2,1%甘氨酸,和0.15%1-羟基苯并三唑。
图1结果表明,当五水硫酸铜(CuSO4·5H2O)加入配方(i),(ii)和(iv)中时,随着Cu2+浓度增加,腐蚀速率显著增加。相反,与含有BTA和羟基BTA的配方比较,ATA在配方(iii)中钝化效果几乎独立于Cu2+浓度变化。由此,ATA在铜CMP浆液组合物中比BTA提供了预料之外的实质性改进,结果证明了ATA作为腐蚀抑制剂的效用,其使得铜在微电子基材上实现了稳定、一致的抛光。
实施例2
对含有ATA溶液的腐蚀能力进行了测量,当采用Ag/AgCl的饱和KCl参比电极时,在0.28-0.35伏特的范围内确定为恒定。这些结果显示,铜在H2O2/甘氨酸/ATA组合物比在H2O2/甘氨酸组合物中热力学更稳定,这是因为后一组合物没有ATA,当采用Ag/AgCl的饱和KCl参比电极测量时,铜的腐蚀能力为0.17伏特。
实施例3
为了评估本发明含ATA抑制剂的CMP浆液,制备不同ATA浓度的浆液组合物。第一部分CMP配方以浆液线1输送,而第二部分CMP配方以浆液线2输送。然后在CMP装置的台板上混合各部分从而生成CMP组合物。
浆液线1中的第一部分CMP配方含有2%Nanotek氧化铝(商购自Nanophase Technologies Corporation,Romeoville,Illinois)的水性介质,pH 3.5。该第一部分CMP配方以125ml/min的流速输送至台板。浆液线2中的第二部分CMP配方含有10%过氧化氢、2%甘氨酸和ATA的去离子水作为溶剂,pH 3.5。该第二部分CMP配方以125ml/min流速输送至台板。ATA在第二部分配方的浓度为最终浆液所需ATA浓度的两倍,这是因为终了浆液是将来自浆液线1和浆液线2的流在台板上混合而产生的。
因此,通过混合来自浆液线1和2的流而产生的终了CMP组合物的最终组成为:5%过氧化氢,1%甘氨酸,1%Nanotek氧化铝研磨剂,以及ATA,pH 3.5。
利用不同浓度ATA的各浆液组合物,对带有膜层的铜包被的硅晶片进行抛光,所述膜层含有c-Si块(bulk)/5,000 TEOS SiO2/250 Ta衬垫/1,000 PVD Cu籽/15,000 ECD Cu,并利用4-点探测器,测量从使用各个相应浆液组合物包被的晶片中铜的去除率。结果示于图2中。
图2示出铜金属的去除率,以/min表示,作为基于CMP浆液组合物总重的ATA浓度(wt%)的函数。结果表明,在ATA浓度为0.15wt.%至0.45wt.%时,铜的去除率为约2200/min至约4500/min,铜去除率一般以线性方式随ATA浓度减少。
实施例4
利用Strasbaugh 6EC抛光工具(可商购自Strasbaugh Corporation,San Luis Obispo,California)对10微米铜线的凹陷进行了研究。抛光垫组件包括IC1000抛光垫和Suba IV副垫(subpad)(可商购自RodelCorporation,Newark,Delaware)。抛光条件包括4psi向下力,工作台和90rpm的载速(carrier speed),以及250ml/min的浆液流速。Sematech(Austin,TX)854压花晶片用于研究独立的铜线和阵列(50%压花密度)铜线的凹陷。
对两种水性浆液铜CMP配方进行测试。配方1含有0.2%BTA,1%氧化铝研磨剂,5%过氧化氢和1%甘氨酸,pH 3.5。配方2含有0.4%ATA,2%甘氨酸,5%过氧化氢和1%氧化铝研磨剂。结果表明,当BTA用作腐蚀抑制剂(配方1)时,终点处(所有铜金属膜皆从晶片上去除)在独立线和阵列线(array line)的凹陷之间有显著的不同。当ATA取代BTA作为腐蚀抑制剂(配方2)时,CMP抛光操作的终点处,独立和阵列10微米线的凹陷程度相同,并且总体凹陷程度基本上降低。
尽管参照本发明的特定方面,特征和例证性实施方案,本发明已进行了描述,但应理解的是,本发明的效用并不限于此,而是延伸并包括其他众多变体,修改和替代的实施方案,以及基于在此公开的内容还给本领域技术人员以提示。因此,本发明旨在要求宽泛的解释,正如在其实质和范围内包括所有这样的变体,修改和替代。
Claims (36)
1.化学机械抛光组合物,其在还包括基于组合物的总重量浓度从0.3wt%到1wt%的CuSO4·5H2O的组合物中测量的Cu的静态蚀刻速率范围从200/min到550/min。
2.权利要求1的化学机械抛光组合物,其中组合物包括甘氨酸和第一腐蚀抑制剂。
3.权利要求2的化学机械抛光组合物,其中组合物的pH为3.5。
4.权利要求2的化学机械抛光组合物,其中组合物还包括氧化剂。
5.权利要求1的化学机械抛光组合物,其中与包含浓度为0.3wt%的CuSO4·5H2O的组合物接触的Cu的静态蚀刻速率的范围从200/min到220/min。
6.权利要求1的化学机械抛光组合物,包含甘氨酸和至少一种腐蚀抑制剂,其中与包含浓度为0.3wt%的CuSO4·5H2O的组合物接触的Cu的静态蚀刻速率的范围从200/min到220/min。
7.权利要求1的化学机械抛光组合物,包含甘氨酸,至少一种腐蚀抑制剂和氧化剂,其中与具有浓度为0.15wt%的腐蚀抑制剂和包含浓度为0.3wt%的CuSO4·5H2O的pH3.5的组合物接触的Cu的静态蚀刻速率的范围从200/min到220/min。
8.权利要求2的化学机械抛光组合物,其中第一腐蚀抑制剂包括5-氨基四唑单水合物。
9.权利要求4的化学机械抛光组合物,其中氧化剂包括至少一种选自下列的试剂:硝酸铁,草酸铁铵,柠檬酸铁铵,高锰酸盐,过氧酸,过硼酸盐,过氧化氢脲,碘酸盐,高氯酸盐,过硫酸盐,溴酸盐,苯醌,氯酸盐,亚氯酸盐,次氯酸盐,次碘酸盐,溴氧化盐,过碳酸盐,高碘酸盐,铈盐,铬酸盐化合物和重铬酸盐化合物,氰铜酸盐和氰铁化物盐,铁菲咯啉,吡啶铁和铁铈齐。
10.权利要求4的化学机械抛光组合物,其中氧化剂包括过氧化氢。
11.权利要求4的化学机械抛光组合物,还包括与甘氨酸组合的第二螯合剂。
12.权利要求4的化学机械抛光组合物,还包括与第一腐蚀抑制剂组合的第二腐蚀抑制剂。
13.权利要求4的化学机械抛光组合物,还包括研磨剂。
14.权利要求4的化学机械抛光组合物,还包括pH调节剂。
15.权利要求4的化学机械抛光组合物,还包括至少一种胺。
16.权利要求4的化学机械抛光组合物,还包括至少一种表面活性剂。
17.权利要求4的化学机械抛光组合物,还包括溶剂。
18.权利要求2的化学机械抛光组合物,其中第一腐蚀抑制剂包括5-氨基四唑单水合物,并且组合物还包括氧化剂和溶剂。
19.权利要求18的化学机械抛光组合物,还包括研磨剂。
20.权利要求13的化学机械抛光组合物,其中研磨剂包括至少一种选自下列的研磨剂:硅石,氧化铝,碳化硅,氮化硅,氧化铁,二氧化铈,氧化锆,氧化锡,二氧化钛,以及氧化铝包被的胶体硅石。
21.权利要求13的化学机械抛光组合物,其中研磨剂包括氧化铝。
22.在其上具有铜的基材上抛光铜的方法,包括将基材上的铜在化学机械抛光条件下与对铜有效抛光的化学机械抛光组合物接触,其中化学机械抛光组合物在还包括基于组合物的总重量浓度从0.3wt%到1wt%的CuSO4·5H2O的组合物中测量的Cu的静态蚀刻速率范围从200/min到550/min。
23.权利要求22的方法,其中所述化学机械抛光组合物还包括甘氨酸和至少一种腐蚀抑制剂。
24.权利要求23的方法,其中所述化学机械抛光组合物还包括至少一种选自研磨剂,氧化剂,溶剂和其组合的组分。
25.权利要求22的方法,其中所述铜位于半导体基材上,并且形成微电子装置的组元,其中所述组元选自互连,触点,导电转接,镀金属,电极,以及场发射器组件用的导电基层。
26.权利要求23的方法,其中所述化学机械抛光组合物还包括研磨剂,氧化剂和溶剂。
27.权利要求26的方法,其中所述化学机械抛光组合物包括含有第一部分和第二部分的两部分配方,所述第一部分包括研磨剂和腐蚀抑制剂的水性介质,而所述第二部分包括氧化剂和甘氨酸,所述方法进一步包括混合第一和第二部分生成所述化学机械抛光组合物。
28.权利要求26的方法,其中所述化学机械抛光组合物包括含有第一部分和第二部分的两部分配方,所述第一部分包括研磨剂,甘氨酸和腐蚀抑制剂的水性介质,而所述第二部分包括氧化剂,所述方法进一步包括混合第一和第二部分生成所述化学机械抛光组合物。
29.权利要求22的方法,其中组合物的pH为3.5。
30.一种生产半导体基材的方法,所述方法包括将基材上的铜在化学机械抛光条件下与对铜有效抛光的化学机械抛光组合物接触,其中化学机械抛光组合物包含5-氨基四唑。
31.权利要求30的方法,其中化学机械抛光组合物还包括螯合剂。
32.权利要求31的方法,其中螯合剂包括选自以下的至少一种氨基酸:甘氨酸,丝氨酸,脯氨酸,亮氨酸,丙氨酸,天冬酰胺,天冬氨酸,谷氨酰胺,缬氨酸,和赖氨酸。
33.权利要求31的方法,其中化学机械抛光组合物还包括至少一种氧化剂。
34.权利要求30的方法,其中化学机械抛光组合物还包括过氧化氢,甘氨酸,研磨剂和水。
35.权利要求30的方法,其中所述铜位于半导体基材上,并形成微电子装置的组元。
36.权利要求35的方法,其中所述组元选自互连,触点,导电转接,镀金属,电极,以及场发射器组件用的导电基层。
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-
2002
- 2002-12-10 US US10/315,641 patent/US7300601B2/en not_active Expired - Lifetime
-
2003
- 2003-12-02 AU AU2003297590A patent/AU2003297590A1/en not_active Abandoned
- 2003-12-02 EP EP03812786A patent/EP1570015A4/en not_active Withdrawn
- 2003-12-02 CN CNB2003801085064A patent/CN1329467C/zh not_active Expired - Lifetime
- 2003-12-02 WO PCT/US2003/038047 patent/WO2004053008A2/en not_active Application Discontinuation
- 2003-12-02 CN CNA2007101065751A patent/CN101085901A/zh active Pending
- 2003-12-09 TW TW092134672A patent/TWI338711B/zh not_active IP Right Cessation
-
2005
- 2005-04-28 US US11/117,282 patent/US20050263490A1/en not_active Abandoned
- 2005-04-28 US US11/117,274 patent/US7361603B2/en not_active Expired - Fee Related
-
2007
- 2007-04-10 US US11/733,410 patent/US20070181852A1/en not_active Abandoned
-
2008
- 2008-09-19 US US12/234,199 patent/US8236695B2/en not_active Expired - Fee Related
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CN105793471A (zh) * | 2013-12-02 | 2016-07-20 | 艺康美国股份有限公司 | 基于四唑的腐蚀抑制剂 |
CN105793471B (zh) * | 2013-12-02 | 2019-11-05 | 艺康美国股份有限公司 | 基于四唑的腐蚀抑制剂 |
WO2017214995A1 (zh) * | 2016-06-17 | 2017-12-21 | 深圳市恒兆智科技有限公司 | 抛光剂、铜件及其抛光处理方法 |
CN110892093A (zh) * | 2017-05-25 | 2020-03-17 | 圣戈本陶瓷及塑料股份有限公司 | 用于陶瓷材料的化学机械抛光的氧化流体 |
CN110256968A (zh) * | 2019-05-29 | 2019-09-20 | 湖南皓志科技股份有限公司 | 一种用于铜抛光的氧化铝抛光液及其制备方法 |
CN114258424A (zh) * | 2019-06-13 | 2022-03-29 | 富士胶片电子材料美国有限公司 | 蚀刻组合物 |
CN114258424B (zh) * | 2019-06-13 | 2023-07-04 | 富士胶片电子材料美国有限公司 | 蚀刻组合物 |
Also Published As
Publication number | Publication date |
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US20090137122A1 (en) | 2009-05-28 |
EP1570015A2 (en) | 2005-09-07 |
WO2004053008A3 (en) | 2004-09-02 |
US8236695B2 (en) | 2012-08-07 |
CN1329467C (zh) | 2007-08-01 |
US20040108302A1 (en) | 2004-06-10 |
AU2003297590A1 (en) | 2004-06-30 |
TW200417600A (en) | 2004-09-16 |
WO2004053008A2 (en) | 2004-06-24 |
CN1735671A (zh) | 2006-02-15 |
US20070181852A1 (en) | 2007-08-09 |
AU2003297590A8 (en) | 2004-06-30 |
US7361603B2 (en) | 2008-04-22 |
EP1570015A4 (en) | 2006-01-25 |
US7300601B2 (en) | 2007-11-27 |
US20050263490A1 (en) | 2005-12-01 |
TWI338711B (en) | 2011-03-11 |
US20050255693A1 (en) | 2005-11-17 |
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