CN116426219A - 一种化学机械抛光液及其应用 - Google Patents
一种化学机械抛光液及其应用 Download PDFInfo
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- CN116426219A CN116426219A CN202111654879.8A CN202111654879A CN116426219A CN 116426219 A CN116426219 A CN 116426219A CN 202111654879 A CN202111654879 A CN 202111654879A CN 116426219 A CN116426219 A CN 116426219A
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Classifications
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- 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
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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
- H01L21/3105—After-treatment
- H01L21/31051—Planarisation of the insulating layers
- H01L21/31053—Planarisation of the insulating layers involving a dielectric removal step
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- H—ELECTRICITY
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- 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
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- H01L21/3212—Planarisation by chemical mechanical polishing [CMP]
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
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- Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
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- Computer Hardware Design (AREA)
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Abstract
本发明提供了一种化学机械抛光液及其使用方法。具体的,所述化学机械抛光液包含研磨颗粒,络合剂,腐蚀抑制剂,羧酸酯类化合物,金属表面缺陷改善剂和氧化剂。本发明中的化学机械抛光液可应用于金属铜互连的抛光,具有较高的金属铜去除速率,并且对钽的去除速率低,从而具有较高的铜/钽去除速率选择比,同时可以改善抛光后铜线的碟形凹陷和介质层侵蚀,并降低抛光后的铜表面粗糙度和表面缺陷数。
Description
技术领域
本发明涉及化学抛光领域,尤其涉及一种化学机械抛光液及其应用。
背景技术
随着半导体技术的发展,电子部件的微小化,铜作为一种具有良好导电性的材料,而被广泛应用于电子元件电路中。由于铜的电阻小,从而可以加快电路中晶体管间信号的传递速度,还可提供更小的寄生电容能力,较小的电迁移的敏感性。这些电学优点都使得铜在半导体技术发展中拥有良好的发展前景。
但在铜的集成电路制造过程中发现,铜会迁移或扩散进入到集成电路的晶体管区域,从而对于半导体的晶体管的性能产生不利影响,因而铜的互连线只能以镶嵌工艺制造,即:在第一层里形成沟槽,在沟槽内填充铜阻挡层和铜,形成金属导线并覆盖在介电层上。然后通过化学机械抛光将介电层上多余的铜/铜阻挡层除去,在沟槽里留下单个互连线。铜的化学机械抛光过程一般分为3个步骤:第1步,先用较高的下压力,以快且高效的去除速率除去衬底表面上大量的铜并留下一定厚度的铜,第2步,用较低的去除速率去除剩余的金属铜并停在阻挡层,第3步,再用阻挡层抛光液去除阻挡层及部分介电层和金属铜,实现平坦化。
铜抛光的过程中,一方面要尽快去除阻挡层上多余的铜,另一方面要尽量减小抛光后铜线的碟形凹陷。在铜抛光前,金属层在铜线上方有部分凹陷。抛光时,介质材料上的铜在较高的主体压力下易于被去除,而凹陷处的铜所受的抛光压力比主体压力低,铜去除速率小。随着抛光的进行,铜的高度差会逐渐减小,达到平坦化。但是在抛光过程中,如果铜抛光液的化学作用太强,静态腐蚀速率太高,则铜的钝化膜即使在较低压力下(如铜线凹陷处)也易于被去除,导致平坦化效率降低,抛光后的碟形凹陷增大。
随着集成电路的发展,一方面,在传统的IC行业中,为了提高集成度,降低能耗,缩短延迟时间,线宽越来越窄,介电层使用机械强度较低的低介电(low-k)材料,布线的层数也越来越多,为了保证集成电路的性能和稳定性,对铜化学机械抛光的要求也越来越高。要求在保证铜的去除速率的情况下降低抛光压力,提高铜线表面的平坦化,控制表面缺陷。另一方面,由于物理局限性,线宽不能无限缩小,半导体行业不再单纯地依赖在单一芯片上集成更多的器件来提高性能,而转向于多芯片封装。
硅通孔(TSV)技术作为一种通过在芯片和芯片之间、晶圆与晶圆之间制作垂直导通,实现芯片之间互连的最新技术而得到工业界的广泛认可。TSV能够使芯片在三维方向堆叠的密度最大,外形尺寸最小,大大改善芯片速度和低功耗的性能。目前的TSV工艺是结合传统的IC工艺形成贯穿硅基底的铜穿孔,即在TSV开口中填充铜实现导通,填充后多余的铜也需要利用化学机械抛光去除达到平坦化。与传统IC工业不同,由于硅通孔很深,填充后表面多余的铜通常有几到几十微米厚。为了快速去除这些多余的铜。通常需要具有很高的铜去除速率,同时抛光后的表面平整度好。而现有的抛光液,在抛光后会产生碟形凹陷、介质层侵蚀,以及铜残留和腐蚀等缺陷。
发明内容
为了克服上述技术缺陷,本发明的目的在于提供一种化学机械抛光液,在CMP过程中实现较高的金属铜薄膜去除率,同时能够改善抛光后铜线的碟形凹陷(dishing)和介质层侵蚀(Erosion)以及铜表面粗糙度,同时抛光后无铜残留和腐蚀等缺陷。
具体的,本发明提供一种化学机械抛光液,包括:研磨颗粒,络合剂,羧酸酯类化合物,金属表面缺陷改善剂,腐蚀抑制剂和氧化剂;所述研磨颗粒为二氧化硅,平均粒径为20-80nm;所述络合剂为氨羧化合物及其盐;所述金属表面缺陷改善剂包括多元醇、亲水性聚合物中的一种或多种;所述腐蚀抑制剂为不含苯环的氮唑类化合物。
优选的,所述二氧化硅研磨颗粒的质量百分比含量为0.05%-1.5%。
优选的,所述络合剂为选自甘氨酸、丙氨酸、天冬氨酸、天冬酰胺、丝氨酸、苏氨酸、酪氨酸、色氨酸、脯氨酸、半胱氨酸、甲硫氨酸、精氨酸、组氨酸中、缬氨酸、亮氨酸、苯丙氨酸、赖氨酸、谷氨酸、谷氨酰胺、氨三乙酸、乙二胺四乙酸、环己烷四乙酸、乙二胺二琥珀酸、二乙烯三胺五乙酸和三乙烯四胺六乙酸中的一种或多种。
优选的,所述络合剂的质量百分比含量为0.1%-3.0%。
优选的,所述羧酸酯类化合物选自三乙醇胺羧酸酯,二乙醇胺羧酸酯,1-甲基咪唑-2-甲酸乙酯,1H-吡咯-3-甲酸甲酯,5-氨基-3-甲基-1H-吡唑-4-甲酸乙酯,3-氨基吡嗪-2-羧酸甲酯,2-氨基-5-甲基噻吩-3-甲酸乙酯,3-氨基异烟酸甲酯,2-溴噻唑-4-甲酸甲酯,5-氨基-3-甲基-2,4-噻酚二羧酸二乙酯,羧酸三氮唑甲酯中的一种或多种。
优选的,所述羧酸酯类化合物的质量百分比含量为0.001%-0.5%。
优选的,所述羧酸酯类化合物的质量百分比含量为0.005%-0.2%。
优选的,所述多元醇包括乙二醇、一缩二乙二醇、甘油中的一种或多种;所述亲水聚合物包括聚乙烯醇,聚乙烯吡咯烷酮,聚丙烯酰胺,聚氧乙烯聚氧丙烯嵌段聚合物中的一种或多种;所述亲水聚合物分子量为1000~10000。
优选的,所述金属表面缺陷改善剂的质量百分比含量为0.001%~2%。
优选的,所述腐蚀抑制剂选自1,2,4-三氮唑、3-氨基-1,2,4-三氮唑、4-氨基-1,2,4-三氮唑、3,5-二氨基-1,2,4-三氮唑、5-羧基-3-氨基-1,2,4-三氮唑、3-氨基-5-巯基-1,2,4-三氮唑、5-乙酸-1H-四氮唑、5-甲基四氮唑和5-氨基-1H-四氮唑中的一种或两种;
优选的,所述不含苯环的氮唑类化合物的质量百分比含量为0.001-0.5%。
优选的,所述氧化剂为过氧化氢;
所述氧化剂的质量百分比含量为0.05%-3.0%。
优选的,所述化学机械抛光液的pH值为5.0-8.0。
本发明的另一方面,提供一种将以上任一所述的化学机械抛光液在金属铜的抛光中的应用。
本发明的化学机械抛光液可以浓缩制备,在使用前用去离子水稀释并添加氧化剂至本发明的浓度范围。
与现有技术相比较,本发明的优势在于:
与现有技术相比,本发明的优势在于:1)本发明的抛光液对铜的去除速率高,对钽的去除速率低,从而具有较高的铜/钽去除速率选择比;2)本发明的抛光液可以改善抛光后铜线的碟型凹陷和介质层侵蚀;3)本发明的抛光液可以改善抛光后铜表面粗糙度和表面缺陷数。
具体实施方式
下面通过具体实施例进一步阐述本发明的优点,但本发明的保护范围不仅仅局限于下述实施例。
应当注意的是,本发明的实施例有较佳的实施性,且并非对本发明作任何形式的限制,任何熟悉该领域的技术人员可能利用上述揭示的技术内容变更或修饰为等同的有效实施例,但凡未脱离本发明技术方案的内容,依据本发明的技术实质对以上实施例所作的任何修改或等同变化及修饰,均仍属于本发明技术方案的范围内。
表1给出了本发明的化学机械抛光液的对比例1-4和实施例1-33化学机械抛光液的各组分及其含量。按表中所给配方,将除氧化剂以外的其他组分混合均匀,用水补足质量百分比至100%。用KOH或HNO3调节到所需要的pH值。使用前加氧化剂,混合均匀即可。本发明的抛光液也可以先配制成浓缩样,在使用时用去离子水进行稀释至表1中所示的浓度,并添加氧化剂使用。
表1实施例1-33与对比例1-4化学机械抛光液的组分及含量
采用对比例1-4和本发明实施例1-33的化学机械抛光液,按照下述条件对空片铜(Cu)、钽(Ta)进行抛光。
具体抛光条件:Cu抛光压力为1.5psi和2.0psi,钽抛光压力为1.5psi;抛光盘及抛光头转速73/67rpm,抛光垫IC1010,抛光液流速300mL/min,抛光机台为12”Reflexion LK,抛光时间为1min。分别测量各实施例对铜/钽的去除速率,并计算二者的去除速率选择比,结果列于表2。
采用对比例1-4和本发明实施例1-33的化学机械抛光液,按照下述条件对含图形的铜晶圆进行抛光。
具体抛光条件:抛光盘及抛光头转速73/67rpm,抛光垫IC1010,抛光液流速300mL/min,抛光机台为12”Reflexion LK。在抛光盘1上用2.0psi的下压力抛光有图案的铜晶片至残留铜约然后再在抛光盘2上用1.5psi的下压力将残留的铜去除。用XE-300P原子力显微镜测量有图案的铜晶片上5um/1um(铜线/介电材料线宽)的铜线阵列区的碟型凹陷值(Dishing),介质层侵蚀(Erosion),以及铜表面粗糙度(Roughness),用表面缺陷扫描仪SP2检测抛光后铜空白晶圆的表面缺陷数,所得的铜线的碟形凹陷值和介质层侵蚀值、以及铜表面粗糙度和表面缺陷数结果列于表2。
表2对比例1~4和实施例1~33化学机械抛光液的抛光测试数据
由表2可见,与对比例相比,本发明实施例的抛光液不仅具有较高的铜/钽去除速率选择比,而且,降低了抛光后铜线的碟形凹陷和介质层侵蚀,抛光后的铜表面粗糙度和表面缺陷数也显著降低。
对比例1的抛光液只含有二氧化硅研磨颗粒、络合剂、氧化剂,对铜、钽的去除速率均较高,因此对铜/钽的去除速率选择比低;对比例2的抛光液在对比例1的基础上添加了不含苯环的氮唑腐蚀抑制剂,从而降低了钽的去除速率,在一定程度上提高了抛光液对铜/钽的去除速率选择比。但是,对比例2的抛光液对铜/钽的去除速率选择比仍然不够高,不能满足钽作为阻挡层时的抛光需要,而且使用对比例2的抛光液抛光后的铜线的碟型凹陷和介质层侵蚀仍然较大。
由对比3-4和实施例1可以看出,选用带有苯环的唑类腐蚀抑制剂苯并三氮唑和磷酸酯类表面活性剂的组合,虽然能降低钽的去除速率,但同时也抑制了铜的去除速率,无法有效地去除铜。由此可知,增加金属表面活性改善剂可以有效改善抛光后铜表面的表面粗糙度和表面缺陷数比较高,但是抛光后的铜碟形凹陷和介质层侵蚀较高。羧酸酯类化合物的加入可以有效改善铜的碟形凹陷和介质层侵蚀。
本发明实施例1-33的抛光液,通过选择平均粒径为20-80nm的二氧化硅研磨颗粒,将pH值控制在5-8,并且将不带苯环的唑类腐蚀抑制剂,羧酸酯类化合物和金属表面缺陷改善剂配合使用,从而具有较高的铜去除速率和较低的钽去除速率,以及较高的铜/钽去除速率选择比;同时,抛光后的铜线的碟型凹陷、介质层侵蚀显著降低,并且抛光后铜表面具有很低的表面粗糙度和表面缺陷数。
应当注意的是,本发明的实施例有较佳的实施性,且并非对本发明作任何形式的限制,任何熟悉该领域的技术人员可能利用上述揭示的技术内容变更或修饰为等同的有效实施例,但凡未脱离本发明技术方案的内容,依据本发明的技术实质对以上实施例所作的任何修改或等同变化及修饰,均仍属于本发明技术方案的范围内。
Claims (14)
1.一种化学机械抛光液,其特征在于,
包括:研磨颗粒,络合剂,羧酸酯类化合物,金属表面缺陷改善剂,腐蚀抑制剂和氧化剂;
所述研磨颗粒为二氧化硅,平均粒径为20-80nm;
所述络合剂为氨羧化合物及其盐;
所述金属表面缺陷改善剂包括多元醇、亲水性聚合物中的一种或多种;
所述腐蚀抑制剂为不含苯环的氮唑类化合物;
所述氧化剂为过氧化氢。
2.根据权利要求1所述化学机械抛光液,其特征在于,
所述二氧化硅研磨颗粒的质量百分比含量为0.05%-1.5%。
3.根据权利要求1所述的化学机械抛光液,其特征在于,
所述络合剂为选自甘氨酸、丙氨酸、天冬氨酸、天冬酰胺、丝氨酸、苏氨酸、酪氨酸、色氨酸、脯氨酸、半胱氨酸、甲硫氨酸、精氨酸、组氨酸中、缬氨酸、亮氨酸、苯丙氨酸、赖氨酸、谷氨酸、谷氨酰胺、氨三乙酸、乙二胺四乙酸、环己烷四乙酸、乙二胺二琥珀酸、二乙烯三胺五乙酸和三乙烯四胺六乙酸中的一种或多种。
4.根据权利要求1所述的化学机械抛光液,其特征在于,
所述络合剂的质量百分比含量为0.1%-3.0%。
5.根据权利要求1所述的化学机械抛光液,其特征在于,
所述羧酸酯类化合物选自三乙醇胺羧酸酯,二乙醇胺羧酸酯,1-甲基咪唑-2-甲酸乙酯,1H-吡咯-3-甲酸甲酯,5-氨基-3-甲基-1H-吡唑-4-甲酸乙酯,3-氨基吡嗪-2-羧酸甲酯,2-氨基-5-甲基噻吩-3-甲酸乙酯,3-氨基异烟酸甲酯,2-溴噻唑-4-甲酸甲酯,5-氨基-3-甲基-2,4-噻酚二羧酸二乙酯,羧酸三氮唑甲酯中的一种或多种。
6.根据权利要求1所述的化学机械抛光液,其特征在于,
所述羧酸酯类化合物的质量百分比含量为0.001%-0.5%。
7.根据权利要求1所述化学机械抛光液,其特征在于,
所述羧酸酯类化合物的质量百分比含量为0.005%-0.2%。
8.根据权利要求1所述化学机械抛光液,其特征在于,
所述多元醇包括乙二醇、一缩二乙二醇、甘油中的一种或多种;
所述亲水聚合物包括聚乙烯醇,聚乙烯吡咯烷酮,聚丙烯酰胺,聚氧乙烯聚氧丙烯嵌段聚合物中的一种或多种;所述亲水聚合物分子量为1000~10000。
9.根据权利要求1所述化学机械抛光液,其特征在于,
所述金属表面缺陷改善剂的质量百分比含量为0.001%~2%。
10.根据权利要求1所述的化学机械抛光液,其特征在于,
所述腐蚀抑制剂选自1,2,4-三氮唑、3-氨基-1,2,4-三氮唑、4-氨基-1,2,4-三氮唑、3,5-二氨基-1,2,4-三氮唑、5-羧基-3-氨基-1,2,4-三氮唑、3-氨基-5-巯基-1,2,4-三氮唑、5-乙酸-1H-四氮唑、5-甲基四氮唑和5-氨基-1H-四氮唑中的一种或两种。
11.根据权利要求1所述的化学机械抛光液,其特征在于,
所述腐蚀抑制剂的质量百分比含量为0.001-0.5%。
12.根据权利要求1所述的化学机械抛光液,其特征在于,
所述氧化剂为过氧化氢;
所述氧化剂的质量百分比含量为0.05%-3.0%。
13.根据权利要求1所述的化学机械抛光液,其特征在于,
所述化学机械抛光液的pH值为5.0-8.0。
14.一种如权利要求1~13任一所述的化学机械抛光液在金属铜的抛光中的应用。
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