CN100362068C - 不含磨料的化学机械抛光组合物及相关方法 - Google Patents
不含磨料的化学机械抛光组合物及相关方法 Download PDFInfo
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- CN100362068C CN100362068C CNB2005101287071A CN200510128707A CN100362068C CN 100362068 C CN100362068 C CN 100362068C CN B2005101287071 A CNB2005101287071 A CN B2005101287071A CN 200510128707 A CN200510128707 A CN 200510128707A CN 100362068 C CN100362068 C CN 100362068C
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- amphiphilic polymer
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- ferrous metal
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- 239000012064 sodium phosphate buffer Substances 0.000 description 1
- GGCZERPQGJTIQP-UHFFFAOYSA-N sodium;9,10-dioxoanthracene-2-sulfonic acid Chemical compound [Na+].C1=CC=C2C(=O)C3=CC(S(=O)(=O)O)=CC=C3C(=O)C2=C1 GGCZERPQGJTIQP-UHFFFAOYSA-N 0.000 description 1
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- 229910052715 tantalum Inorganic materials 0.000 description 1
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 description 1
- MZLGASXMSKOWSE-UHFFFAOYSA-N tantalum nitride Chemical compound [Ta]#N MZLGASXMSKOWSE-UHFFFAOYSA-N 0.000 description 1
- 229940095064 tartrate Drugs 0.000 description 1
- MDDUHVRJJAFRAU-YZNNVMRBSA-N tert-butyl-[(1r,3s,5z)-3-[tert-butyl(dimethyl)silyl]oxy-5-(2-diphenylphosphorylethylidene)-4-methylidenecyclohexyl]oxy-dimethylsilane Chemical compound C1[C@@H](O[Si](C)(C)C(C)(C)C)C[C@H](O[Si](C)(C)C(C)(C)C)C(=C)\C1=C/CP(=O)(C=1C=CC=CC=1)C1=CC=CC=C1 MDDUHVRJJAFRAU-YZNNVMRBSA-N 0.000 description 1
- VKFFEYLSKIYTSJ-UHFFFAOYSA-N tetraazanium;phosphonato phosphate Chemical compound [NH4+].[NH4+].[NH4+].[NH4+].[O-]P([O-])(=O)OP([O-])([O-])=O VKFFEYLSKIYTSJ-UHFFFAOYSA-N 0.000 description 1
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- 239000010936 titanium Substances 0.000 description 1
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- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- LRXTYHSAJDENHV-UHFFFAOYSA-H zinc phosphate Chemical compound [Zn+2].[Zn+2].[Zn+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O LRXTYHSAJDENHV-UHFFFAOYSA-H 0.000 description 1
- 229910000165 zinc phosphate Inorganic materials 0.000 description 1
- OMSYGYSPFZQFFP-UHFFFAOYSA-J zinc pyrophosphate Chemical compound [Zn+2].[Zn+2].[O-]P([O-])(=O)OP([O-])([O-])=O OMSYGYSPFZQFFP-UHFFFAOYSA-J 0.000 description 1
- CZPRKINNVBONSF-UHFFFAOYSA-M zinc;dioxido(oxo)phosphanium Chemical compound [Zn+2].[O-][P+]([O-])=O CZPRKINNVBONSF-UHFFFAOYSA-M 0.000 description 1
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- C09G—POLISHING COMPOSITIONS; SKI WAXES
- C09G1/00—Polishing compositions
- C09G1/02—Polishing compositions containing abrasives or grinding agents
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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
- H01L21/70—Manufacture or treatment of devices consisting of a plurality of solid state components formed in or on a common substrate or of parts thereof; Manufacture of integrated circuit devices or of parts thereof
- H01L21/71—Manufacture of specific parts of devices defined in group H01L21/70
- H01L21/768—Applying interconnections to be used for carrying current between separate components within a device comprising conductors and dielectrics
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- H01L21/30—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26
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- H01L21/30—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26
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- H01L21/306—Chemical or electrical treatment, e.g. electrolytic etching
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- H01L21/30—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26
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- H01L21/3205—Deposition of non-insulating-, e.g. conductive- or resistive-, layers on insulating layers; After-treatment of these layers
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Abstract
一种不含磨料的水性组合物,适用于化学机械抛光含有色金属的有图案的半导体晶片。该组合物包含氧化剂,对有色金属的抑制剂,0-15重量%的水溶性改性纤维素,0-15重量%的磷化合物,0.005-5重量%的两亲聚合物以及水,该两亲聚合物具有碳原子数为2-250的离子性亲水链段。
Description
技术领域
本发明涉及半导体晶片材料的化学机械抛光(CMP),更具体地说,涉及在介电材料与阻挡材料存在条件下,用于抛光半导体晶片上金属互连件的CMP组合物和方法。
背景技术
具体地说,半导体晶片是具有介电层的硅晶片,介电层上包括许多沟槽,排列成位于介电层中的电路互连布线图。布线图设计通常具有镶嵌结构或双重镶嵌结构。阻挡层覆盖图形的介电层,金属层覆盖该阻挡层。该金属层至少具有足够的厚度,能用金属填充有图案的沟槽,形成电路互连。
CMP工艺一般包括多个抛光步骤。例如,第一步以初始高速除去过量的互连金属,如铜。第一步除去之后,第二步抛光能除去残留在阻挡层上位于金属互连之外的金属。后续的除去步骤从半导体晶片的下层介电层上除去阻挡材料,在介电层和金属互连上提供平坦的抛光表面。
位于半导体基材的沟或槽中的金属提供了形成金属电路的金属线路。需要克服的一个问题是,抛光操作倾向于从每个沟或槽中除去金属,导致这些金属出现凹陷。凹陷是不利的,因为它会导致金属电路的关键尺寸发生变化。为了减少凹陷情况,要以较低的抛光压力进行抛光。但是,只降低抛光压力会需要延长抛光时间;在整个拉长的时期内还会出现凹陷情况。
Schroeder等人在美国专利公开第2003/0228763号中公开了一种方法,使用两亲非离子性表面活性剂来处置铜凹陷和介电材料侵蚀的情况。随着有图案的晶片抛光技术向缩小线路宽度的方向发展,不断需要一种方法来减少沟或槽中金属凹陷,同时无须延长抛光操作的时间。而且,需要这样的抛光组合物,在短时间抛光之后形成扫除了互连金属残留物的表面。
发明内容
本发明一方面提供了一种不含磨料的水性组合物,适用于化学机械抛光含有色金属的有图案的半导体晶片,该组合物包含氧化剂,对有色金属的抑制剂,0-15重量%的水溶性改性纤维素,0-15重量%的磷化合物,0.005-5重量%的两亲聚合物和水,所述两亲聚合物具有碳原子数为2-250的离子亲水部分。
本发明另一方面提供了一种不含磨料的水性组合物,适用于化学机械抛光含有色金属的有图案的半导体晶片,该组合物包含0-25重量%的氧化剂,0.05-1 5重量%对有色金属的抑制剂,0-15重量%对有色金属的络合剂,0.01-5重量%的水溶性改性纤维素,0.01-10重量%磷化合物,0.01-3重量%的两亲聚合物和水,所述两亲聚合物具有碳原子数为5-100的离子亲水部分,且数均分子量为50-4000。
本发明另一方面提供了一种化学机械抛光含有色金属的有图案的半导体晶片的方法,该方法包括:a)使晶片与抛光组合物接触,该抛光组合物包含氧化剂,对有色金属的抑制剂,0-15重量%的水溶性改性纤维素,0-15重量%的磷化合物,0.005-5重量%的两亲聚合物和水,所述两亲聚合物具有碳原子数为2-250的离子亲水部分;和b)用抛光垫抛光该晶片。
附图说明
附图1是清除时间的图示。
具体实施方式
本发明组合物和方法在对半导体晶片进行CMP处理,且抛光组合物中含有两亲聚合物时,能提供良好的金属除去速率并能充分清除金属,金属互连的凹陷情况非常轻微。该组合物中任选含有水溶性改性纤维素,水混溶的有机溶剂,和磷化合物。该溶液中不含磨料,也不需要任何磨料。
在本说明书中,该两亲聚合物是指包括疏水性链段和亲水性链段的嵌段共聚物。疏水性链段可以是碳原子数为2-250的聚合链。为了说明本发明,碳原子数表示亲水性链段中的碳原子数。优选碳原子数为5-100,最优选为5-50。亲水性链段是离子性的。亲水性链段中单体单元数优选在1-100。该组合物中含有0.005-5重量%的这些两亲聚合物是有利的。优选组合物中含有0.01-3重量%的这些两亲聚合物。最优选该组合物中含有0.05-2重量%的这些两亲聚合物。
两亲聚合物优选的数均分子量是50-5000——这种表达是指以数均分子量表达的两亲聚合物的分子量。更优选该数均分子量是50-4000,最优选该数均分子量是100-3000。离子性链段包括阳离子,阴离子,和两性的(两性聚电解质和聚内铵盐)。较好地,亲水性链段是阴离子的,如聚丙烯酸或聚甲基丙烯酸。亲水性链段优选包括聚丙烯酸,聚甲基丙烯酸或丙烯酸和甲基丙烯酸的共聚物。共聚物中这些链段的组合产生了性质不同于其各自均聚物的分子,有助于清除金属而不使金属互连出现过度凹陷。该聚合物的疏水端可以包含烃链或烷基硫醇。最优选这些疏水性和亲水性链段以共聚物形式组合。
任选地,组合物含有0-10重量%的水混溶的有机溶剂——本说明书指以重量百分比的所有组成。这些水混溶性有机溶剂通常是醇类或酮类,如甲醇,乙醇,1-丙醇,2-丙醇,乙二醇,1,2-丙二醇,丙三醇,丙酮和甲基乙基酮中的至少一种。该组合物中含有0.005-10重量%的这些有机溶剂是有利的。较好地,该组合物含有0.01-7.5重量%的这些有机溶剂。最好该组合物含有0.02-5重量%的这些有机溶剂。
虽然本发明特别适用于铜互连,但是这种含水抛光组合物也能对其他有色金属互连,如铝,金,镍,铂族金属,银,钨,及其合金进行强化抛光。
任选地,组合物含有0-15重量%的水溶性纤维素。较好地,组合物含有0.01-5.0重量%的水溶性纤维素。最好,该组合物含有0.05-1.5重量%的水溶性纤维素。改性纤维素的实例是阴离子性树胶,如洋菜胶,阿拉伯胶,印度胶,刺梧桐树胶,瓜尔胶,果胶,刺槐豆胶,黄蓍胶,罗望子胶,角叉胶和黄原胶,改性淀粉,褐藻酸,甘露糖醛酸,古洛糖醛酸,以及它们的衍生物和共聚物。优选的水溶性纤维素,羧甲基纤维素(CMC)具有0.1-3.0的取代度,重均分子量为1K-1000K。更好地,CMC具有0.7-1.2的取代度,重均分子量为40K-250K。CMC的取代度是纤维素分子中每个葡糖酐单元上的羟基数目。可以将其认为是CMC中羧酸基“密度”的度量。
该溶液中含有氧化剂。较好地,溶液中含有0-25重量%的氧化剂。更好地,氧化剂在5-10重量%范围。氧化剂能特别有效地帮助溶液在低pH范围除去铜。氧化剂可以是许多氧化性化合物中的至少一种,比如过氧化氢(H2O2),单过硫酸盐,碘酸盐,过邻苯二甲酸镁,过乙酸和其他过酸,过硫酸盐,溴酸盐,高碘酸盐,硝酸盐,铁盐,铈盐,Mn(III)盐,Mn(IV)盐和Mn(VI)盐,银盐,铜盐,铬盐,钴盐,卤素,次氯酸盐以及它们的混合物。而且,使用氧化性化合物的混合物一般是有利的。抛光浆料中含有不稳定的氧化剂时,如过氧化氢,在使用时将该氧化剂混入组合物一般是最有利的。
此外,该溶液中含有抑制剂,通过静态蚀刻(static etch)或其他清除机理来控制有色金属的去除,如铜互连的除去速率。调节抑制剂的浓度,通过保护金属避免发生静态蚀刻来调节互连金属的除去速率。较好地,溶液含有0.05-15重量%的抑制剂。最好该溶液含有0.2-1.0重量%的抑制剂。抑制剂可以由抑制剂混合物构成。吡咯抑制剂对铜和银互连是特别有效的。典型的吡咯抑制剂包括苯并三唑(BTA),巯基苯并噻唑(MBT),甲苯基三唑(TTA)和咪唑。吡咯抑制剂的混合能提高或降低铜的除去速率。BTA是对铜和银特别有效的抑制剂。
除了抑制剂之外,组合物可任选含有对有色金属的络合剂。该络合剂有利于提高金属薄膜如铜的除去速率。较好地,该组合物含有0-15重量%的对有色金属的络合剂。最好,该组合物含有0.1-1重量%的对有色金属的络合剂。络合剂的实例包括乙酸,柠檬酸,乙酰乙酸乙酯,乙醇酸,乳酸,苹果酸,草酸,水杨酸,二硫代氨基甲酸二乙酯钠,琥珀酸,酒石酸,巯基乙酸,甘氨酸,丙氨酸,天冬氨酸,乙二胺,三甲基二胺,丙二酸,戊二酸,3-羟基丁酸,丙酸,邻苯二甲酸,间苯二甲酸,3-羟基水杨酸,3,5-二羟基水杨酸,五倍子酸,葡糖酸,焦儿茶酚,焦棓酚,单宁酸,包括它们的盐及混合物。较好地,络合剂选自乙酸,柠檬酸,乙酰乙酸乙酯,乙醇酸,乳酸,苹果酸,草酸及其混合物。最优选的络合剂是苹果酸。
任选地,组合物含有0-15重量%的含磷化合物。为了说明本发明,“含磷”化合物是含有磷原子的任何化合物。优选的含磷化合物是,如磷酸盐,焦磷酸盐,多磷酸盐,膦酸盐,包括它们的酸,盐,混合酸盐,酯,偏酯,混合酯,以及它们的混合物,如磷酸。特别是,可以用如以下的含磷化合物配制优选的含水抛光组合物:磷酸锌,焦磷酸锌,聚磷酸锌,膦酸锌,磷酸铵,焦磷酸铵,多磷酸铵,膦酸铵,磷酸二铵,焦磷酸二铵,多磷酸二铵,膦酸二铵,磷酸胍,焦磷酸胍,多磷酸胍,膦酸胍,磷酸铁,焦磷酸铁,多磷酸铁,膦酸铁,磷酸铈,焦磷酸铈,多磷酸铈,膦酸铈,磷酸乙二胺,磷酸哌嗪,焦磷酸哌嗪,膦酸哌嗪,磷酸密胺,磷酸二密胺,焦磷酸密胺,多磷酸密胺,膦酸密胺,磷酸蜜白胺,焦磷酸蜜白胺,多磷酸蜜白胺,膦酸蜜白胺,磷酸蜜勒胺,焦磷酸蜜勒胺,多磷酸蜜勒胺,膦酸蜜勒胺,磷酸双氰胺,磷酸脲,包括其酸,盐,混合酸盐,酯,偏酯,混合酯,及其混合物。还可以用氧膦,硫膦,phosphorinane,膦酸盐,亚磷酸盐和次膦酸盐,包括其酸,盐,混合酸盐,酯,偏酯和混合酯。优选的含磷化合物是磷酸铵。
本发明抛光组合物中含磷化合物以能在低压条件下有效提高抛光速率的量存在是有利的。我们相信,抛光组合物中甚至是痕量的含磷化合物也能有效地抛光铜。使用为组合物的0.01-10重量%含磷化合物,能在可接受的抛光压力条件下获得满意的抛光速率。优选的含磷化合物范围是组合物的0.1-5重量%。最好,含磷化合物是组合物的0.3-2重量%。
该化合物能在含余量水的溶液中在宽pH范围内发挥功效。该溶液的适用pH范围从至少2扩展到5。此外,该溶液依赖余量的去离子水,以限制附带的杂质。本发明抛光液的pH优选为2-4,更优选pH是2.5-4。用来调节本发明组合物pH的酸是,如硝酸,硫酸,盐酸,磷酸等。用于调节本发明组合物pH的碱的实例是,如氢氧化铵和氢氧化钾。
本发明的组合物适用于任何含有导电金属,阻挡层或衬里薄膜以及下层介电层的半导体晶片,所述导电金属是如铜,铝,钨,铂,钯,金或铱;所述阻挡层或衬里薄膜是如钽,氮化钽,钛或氮化钛。为了说明本发明,术语“介电材料”指介电常数k的半导体材料,包括低k和超低k介电材料。该组合物和方法在防止侵蚀多种晶片组成材料方面具有极大的优势,如多孔和无孔的低k介电材料,有机和无机低k介电材料,有机硅酸盐玻璃(OSG),氟硅酸盐玻璃(FSG),碳掺杂氧化物(CDO),原硅酸四乙酯(TEOS)和从TEOS衍生的二氧化硅。本发明的组合物还可以用于ECMP(电化学机械抛光)。
本发明优选实施方式
在以下实施例中具体说明本发明的一些实施方式。在这些实施例中,通过重量分析确定共聚组合物的固体重量百分比。使用TSK-GEL pn/08025 GMPWx和TSK-GEL pn/08020 G2500PWx系列柱以及折射率检测器和磷酸钠缓冲洗脱液,通过含水凝胶渗透色谱法确定数均分子量。
实施例1:制备十二烷基硫醇端基的丙烯酸嵌段共聚物;C12S-(AA)30
在配备有机械搅拌器,温度控制装置,冷凝器,单体进料管,催化剂进料管,链转移剂进料管和氮气吹扫装置的1升四颈圆底反应烧瓶中进行聚合反应。按照以下顺序加入这些组分。向烧瓶中投入190克叔丁醇,在氮气吹扫条件下加热到80-82℃。在单体供料罐中装入50克叔丁醇和192.6克丙烯酸。在链转移剂供料罐中装入10克叔丁醇和19.0克正十二烷基硫醇。在引发剂供料罐中装入24克叔丁醇和4.8克过氧新戊酸叔丁酯。达到82℃时,同时开始供应上述三种物料。以2.1克/分的速率供给单体2小时。以0.25克/分的速率供给链转移剂2小时。以0.21克/分的速率供给引发剂2小时。保持反应在80-82℃。供料完成时,在单体供料罐中加入5克叔丁醇,并供给反应烧瓶中。在链转移剂供料罐中加入5克叔丁醇,并供给该反应烧瓶中。在引发剂供料罐中加入7克叔丁醇,并供应至该反应烧瓶中。然后在1小时内向该反应烧瓶中供应202克去离子水,同时保持温度为80-82℃。将反应冷却至65℃,通过添加硫酸亚铁,过氧化叔丁基和甲醛次硫酸钠来还原残余的单体。将反应冷却至室温。制得固体含量为29.3重量%的澄清溶液。通过含水凝胶渗透色谱法测得数均分子量为2134。在真空烘箱中室温干燥该溶液过夜,获得白色固体。
实施例2:制备十二烷基硫醇端基的丙烯酸嵌段共聚物C12-S-(AA)10
在配备有机械搅拌器,温度控制装置,冷凝器,单体进料管,催化剂进料管,链转移剂进料管和氮气吹扫装置的1升四颈圆底反应烧瓶中进行聚合反应。按照以下顺序加入这些组分。向烧瓶中投入190克叔丁醇,在氮气吹扫条件下加热到80-82℃。在单体供料罐中装入50克叔丁醇和192.6克丙烯酸。在链转移剂供料罐中装入30克叔丁醇和53.1克正十二烷基硫醇。在引发剂供料罐中装入24克叔丁醇和4.8克过氧新戊酸叔丁酯。达到82℃时,同时开始供应上述三种物料。以2.1克/分的速率供给单体2小时。以0.70克/分的速率供给链转移剂2小时。以0.21克/分的速率供给引发剂2小时。保持反应在80-82℃。供料完成时,在单体供料罐中加入5克叔丁醇,并供应至该反应烧瓶中。在链转移剂供料罐中添加5克叔丁醇,并供应至该反应烧瓶中。在引发剂供料罐中添加7克叔丁醇,并供应至该反应烧瓶中。然后向该反应烧瓶中添加240克叔丁醇,并将反应在80-82℃保持1小时。将反应冷却至室温。制得固体含量为30.1重量%的澄清溶液。通过含水凝胶渗透色谱法测得数均分子量为796。在真空烘箱中室温干燥该溶液过夜,获得白色固体。
实施例3:制备十二烷基硫醇端基的甲基丙烯酸嵌段共聚物C12-S-(MAA)30
在配备有机械搅拌器,温度控制装置,冷凝器,单体进料管,催化剂进料管,链转移剂进料管和氮气吹扫装置的1升四颈圆底反应烧瓶中进行聚合反应。按照以下顺序加入这些组分。向烧瓶中投入入190克1-丙醇,在氮气吹扫条件下加热到80-82℃。向单体供料罐中装入50克1-丙醇和192.6克甲基丙烯酸。向链转移剂供料罐中装入10克1-丙醇和16.0克正十二烷基硫醇。向引发剂供料罐中装入24克1-丙醇和4.8克过氧新戊酸叔丁酯。达到82℃时,同时开始供应上述三种物料。以2.1克/分的速率供给单体2小时。以0.25克/分的速率供给链转移剂2小时。以0.21克/分的速率供给引发剂2小时。保持反应在80-82℃。供料完成时,在单体供料罐中加入5克叔丁醇,并供应至该反应烧瓶中。在链转移剂供料罐中加入5克叔丁醇,并供应至该反应烧瓶中。在引发剂供料罐中添加7克叔丁醇,并供应至该反应烧瓶中。然后向该反应烧瓶中添加299.5克1-丙醇,将反应在80-82℃保持1小时。将反应冷却至室温。制得固体含量为29.9重量%的澄清溶液。通过含水凝胶渗透色谱法测得数均分子量为2347。在真空烘箱中室温干燥该溶液过夜,获得白色固体。
实施例4:制备十二烷基硫醇端基的甲基丙烯酸嵌段共聚物C12-S-(MAA)10
在配备有机械搅拌器,温度控制装置,冷凝器,单体进料管,催化剂进料管,链转移剂进料管和氮气吹扫装置的1升四颈圆底反应烧瓶中进行聚合反应。按照以下顺序加入这些组分。向烧瓶中装入190克1-丙醇,在氮气吹扫条件下加热到80-82℃。向单体供料罐中装入50克1-丙醇和192.6克甲基丙烯酸。向链转移剂供料罐中装入30克1-丙醇和44.6克正十二烷基硫醇。向引发剂供料罐中装入24克1-丙醇和4.8克过氧新戊酸叔丁酯。达到82℃时,同时开始供应上述三种物料。以2.1克/分的速率供给单体2小时。以0.62克/分的速率供给链转移剂2小时。以0.21克/分的速率供给引发剂2小时。保持反应在80-82℃。供料完成时,在单体供料罐中加入5克叔丁醇,并供应至该反应烧瓶中。在链转移剂供料罐中加入5克叔丁醇,并供应至该反应烧瓶中。在引发剂供料罐中加入7克叔丁醇,并供应至该反应烧瓶中。将反应在80-82℃保持1小时。将反应冷却至室温。制得固体含量为45.3重量%的澄清溶液。通过含水凝胶渗透色谱法测得数均分子量为1144。在真空烘箱中室温干燥该溶液过夜,获得白色固体。
实施例5:制备十八烷基硫醇端基的甲基丙烯酸嵌段共聚物C18-S-(MAA)30
在配备有机械搅拌器,温度控制装置,冷凝器,单体进料管,催化剂进料管,链转移剂进料管和氮气吹扫装置的1升四颈圆底反应烧瓶中进行聚合反应。按照以下顺序加入这些组分。向烧瓶中装入180克叔丁醇,在氮气吹扫条件下加热到80-82℃。向单体供料罐中装入50克叔丁醇和192.6克丙烯酸。在蒸汽浴上将25.1克十八烷基硫醇溶解在20克叔丁醇中,然后投入链转移剂供料罐中。向引发剂供料罐中装入24克叔丁醇和4.8克过氧新戊酸叔丁酯。达到82℃时,同时开始供应上述三种物料。以2.1克/分的速率供给单体2小时。以0.62克/分的速率供给链转移剂2小时。以0.21克/分的速率供给引发剂2小时。保持反应在80-82℃。供料完成时,在单体供料罐中加入5克叔丁醇,并供应至该反应烧瓶中。在链转移剂供料罐中加入15克叔丁醇,并供应至该反应烧瓶中。在引发剂供料罐中加入7克叔丁醇,并供应至该反应烧瓶中。然后在该反应烧瓶中加入202克去离子水,将反应在80-82℃保持1小时。将反应冷却至65℃,通过加入硫酸亚铁,过氧化叔丁基和甲醛次硫酸钠来还原残余的单体。将反应冷却至室温。制得固体含量为28.6重量%的澄清溶液。没有表征数均分子量。在真空烘箱中室温干燥该溶液过夜,获得白色固体。
实施例6:抛光速率
在该实施例中,所有组合物中都含有0.50重量%的BTA,0.22重量%的苹果酸,0.32重量%的羧甲基纤维素(CMC),1.0重量%的甲醇,0.10重量%的两亲聚合物,0.50重量%的磷酸铵,9.00重量%的pH为3.5的过氧化氢——用硝酸调节了pH,以及余量的去离子水。用IPEC 472抛光机,在压力(downforce)条件下使用IC 1000TM聚氨酯抛光垫Rohm and Haas Electronic Materials,CMP Technologies),抛光溶液流速为160立方厘米/分,压板速度为80转/分,托架速度为75转/分,来抛光铜片晶片,确定以埃/分钟为单位的除去速率。用Kinik金刚石磨盘修整抛光垫。
表1
浆料 | 压力(磅/平方英寸) | 压力(千帕) | 两亲聚合物 | 温度(℃) | Cu除去速率(埃/分) |
1 | 1 | 6.9 | C<sub>12</sub>-S-(AA)<sub>30</sub> | 25.5 | 674 |
2 | 2 | 13.8 | C<sub>12</sub>-S-(AA)<sub>30</sub> | 31.7 | 2644 |
3 | 3 | 20.7 | C<sub>12</sub>-S-(AA)<sub>30</sub> | 36.1 | 4911 |
4 | 1 | 6.9 | C<sub>12</sub>-S-(MAA)<sub>30</sub> | 26.7 | 958 |
5 | 2 | 13.8 | C<sub>12</sub>-S-(MAA)<sub>30</sub> | 70.2 | 3655 |
6 | 3 | 20.7 | C<sub>12</sub>-S-(MAA)<sub>30</sub> | 35.5 | 6023 |
以上数据说明,两亲聚合物C12-S-(AA)30和C12-S-(MAA)30分别提供可接受的铜除去速率;那些烷基硫醇/甲基丙烯酸共聚物,如C12-S-(MAA)30提供最大增幅的除去速率。
实施例7:抛光清除速率
在该实施例中,所有组合物中都含有0.50重量%的BTA,0.22重量%的苹果酸,0.32重量%的羧甲基纤维素(CMC),1.00重量%的甲醇,0.50重量%的磷酸铵,9.00重量%的pH为3.5的过氧化氢——用硝酸调节了pH,以及余量的去离子水。
实验测定了铜抛光速率并确定以中等压力从半导体晶片上残余铜的清除率。具体地说,该实验测量了使用0.1重量%的Rohm and Haas聚合物十二烷基硫醇端基的甲基丙烯酸嵌段共聚物C12-S-(MAA)30对抛光速率,清除时间和残余铜清除率的影响。清除时间被定义为EPD2-EPD1(以秒为单位),其中EPD1是通过铜层检测到阻挡层第一信号时的初始点检测时间。EPD2是检测器只检测到阻挡层时的检测时间。图1图示了清除时间的这种定义。利用配备有ISRM检测系统的Applied Materials,Inc.Marra 200毫米抛光机,在2磅/平方英寸(13.8千帕)的压力条件下,用IC1010TM聚氨酯抛光垫(Rohm and HaasElectronic Materials CMP Inc.),以150立方厘米/分钟的抛光液流速,80转/分的压板速度和40转/分的托架速度,来平坦化这些样品。用Kinik金刚石磨盘修整抛光垫。
用硫醇链转移剂和甲基丙烯酸通过溶液聚合反应制备Rohm and Haas聚合物C12-S-(MAA)30。这种特定共聚物针对低分子量。它是一种低分子量嵌段共聚物。
表2
浆料 | 非糖类聚合物(0.1重量%) | 金属RR埃/分 | 90%凹陷埃 | 50微米凹陷埃 | 90/10凹陷埃 | 100/1凹陷埃 | 100微米凹陷埃 | 清除时间(秒)EPD2-EPD1 |
A | PAA/MAA* | 4074 | 237 | 219 | 425 | 390 | 246 | 70 |
7 | C<sub>12</sub>-S-(MAA)<sub>30</sub> | 3813 | 218 | 186 | 319 | 284 | 187 | 93 |
*聚丙烯酸/甲基丙烯酸共聚物(3∶2比例,23K分子量)
如表2中所示,加入0.10重量%的Rohm and Haas共聚物C12-S-(MAA)30产生良好的铜清除速率以及低凹陷。该两亲聚合物在抛光高密度铜部件方面特别有效。
Claims (10)
1.一种不含磨料的水性组合物,它用于化学机械抛光含有色金属的有图案的半导体晶片,所述组合物包含氧化剂、用于所述有色金属的抑制剂、0-15重量%的水溶性改性纤维素、0-15重量%的磷化合物、0.005-5重量%的两亲聚合物、以及水,其中,该两亲聚合物的数均分子量为50-4000,并具有碳原子数为5-100的离子亲水部分。
2.如权利要求1所述的组合物,其特征在于,该两亲聚合物的数均分子量为100-3000。
3.如权利要求2所述的组合物,其特征在于,该两亲聚合物是由丙烯酸或甲基丙烯酸形成的共聚物。
4.如权利要求1所述的组合物,其特征在于,该两亲聚合物是烷基硫醇/甲基丙烯酸嵌段共聚物。
5.一种不含磨料的水性组合物,它用于化学机械抛光含有色金属的有图案的半导体晶片,该组合物包含0-25重量%的氧化剂、0.05-15重量%的用于所述有色金属的抑制剂、0-15重量%的用于所述有色金属的络合剂、0.01-5重量%的水溶性改性纤维素、0.01-10重量%的磷化合物、0.01-3重量%的两亲聚合物、以及水,该两亲聚合物具有碳原子数为5-100的离子亲水部分,其数均分子量为50-4000。
6.如权利要求5所述的组合物,其特征在于,该两亲聚合物的数均分子量为100-3000。
7.如权利要求5所述的组合物,其特征在于,该两亲聚合物是由丙烯酸或甲基丙烯酸形成的共聚物。
8.如权利要求5所述的组合物,其特征在于,该两亲聚合物是烷基硫醇/甲基丙烯酸共聚物。
9.一种化学机械抛光含有色金属的有图案的半导体晶片的方法,该方法包括以下步骤:a)使所述晶片与抛光组合物接触,该抛光组合物包含氧化剂、用于有色金属的抑制剂、0-15重量%的水溶性改性纤维素、0-15重量%的磷化合物、0.005-5重量%的两亲聚合物、以及水,该两亲聚合物的数均分子量为50-4000,并具有碳原子数为5-100的离子亲水部分;以及b)用抛光垫对该晶片进行抛光。
10.如权利要求9所述的方法,其特征在于,晶片与抛光组合物接触,从该有图案的半导体晶片上清除铜。
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