CN110997236A - 整合研磨抛光垫及制造方法 - Google Patents

整合研磨抛光垫及制造方法 Download PDF

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CN110997236A
CN110997236A CN201880051442.5A CN201880051442A CN110997236A CN 110997236 A CN110997236 A CN 110997236A CN 201880051442 A CN201880051442 A CN 201880051442A CN 110997236 A CN110997236 A CN 110997236A
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polishing
abrasive particles
droplets
precursor
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A·库马
A·乔卡里汉
S·嘎纳帕西亚潘
R·巴贾杰
傅博诣
D·莱德菲尔德
N·B·帕蒂班德拉
M·D·科尔内霍
A·辛哈
Y·赵
R·R·阿内帕利
F·C·雷德克
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B24—GRINDING; POLISHING
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    • B24B37/24—Lapping pads for working plane surfaces characterised by the composition or properties of the pad materials
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B24—GRINDING; POLISHING
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    • B24D11/00—Constructional features of flexible abrasive materials; Special features in the manufacture of such materials
    • B24D11/04—Zonally-graded surfaces
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B24—GRINDING; POLISHING
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    • B24D18/00—Manufacture of grinding tools or other grinding devices, e.g. wheels, not otherwise provided for
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    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
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    • B29C64/00—Additive manufacturing, i.e. manufacturing of three-dimensional [3D] objects by additive deposition, additive agglomeration or additive layering, e.g. by 3D printing, stereolithography or selective laser sintering
    • B29C64/10—Processes of additive manufacturing
    • B29C64/106—Processes of additive manufacturing using only liquids or viscous materials, e.g. depositing a continuous bead of viscous material
    • B29C64/112—Processes of additive manufacturing using only liquids or viscous materials, e.g. depositing a continuous bead of viscous material using individual droplets, e.g. from jetting heads
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B33—ADDITIVE MANUFACTURING TECHNOLOGY
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    • B33Y10/00—Processes of additive manufacturing
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B33—ADDITIVE MANUFACTURING TECHNOLOGY
    • B33Y—ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3-D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3-D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
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    • 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
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Abstract

本文所述的实施例涉及整合研磨(IA)抛光垫，以及制造IA抛光垫的方法，所述方法在增材制造工艺(诸如3D喷墨打印工艺)中至少部分使用表面官能化的研磨颗粒。在一个实施例中，形成抛光制品的方法包括：分配第一前驱物的第一多个液滴；固化所述第一多个液滴以形成第一层，所述第一层包括子抛光元件的一部分；将所述第一前驱物及第二前驱物的第二多个液滴分配至所述第一层上；以及固化所述第二多个液滴以形成第二层，所述第二层包括所述子抛光元件的部分与多个抛光元件的部分。在此，所述第二前驱物包括官能化的研磨颗粒，所述官能化的研磨颗粒具有化学结合至所述官能化的研磨颗粒的表面的可聚合基团。

Description

整合研磨抛光垫及制造方法
背景技术
技术领域
本公开内容的实施例总体涉及抛光垫以及形成抛光垫的方法，并且更具体地，涉及用于在电子器件制造工艺中抛光基板的抛光垫。
相关技术的描述
化学机械抛光(CMP)常用于高密度集成电路的制造，以通过使待平坦化的材料层与抛光垫接触并在抛光流体和研磨颗粒存在下移动所述抛光垫和/或基板(并从而移动所述材料层表面)，来平坦化或抛光在基板上所沉积的材料层。CMP的两种常见应用为：主体膜(bulk film)的平坦化，例如前金属介电质(PMD)或层间介电质(ILD)抛光，其中下面的特征在层表面中产生凹槽和突起；以及浅沟槽隔离(STI)和层间金属互连抛光，其中抛光用于从层的暴露表面(域)移除通孔(via)、接触件或沟槽填充材料，所述层具有所述特征。
在典型的CMP工艺中，将基板保持在承载头中，所述承载头将基板的背侧压向抛光垫。通过化学活动和机械活动的组合，跨与抛光垫接触的材料层表面移除材料，所述化学活动和所述机械活动是由抛光流体和研磨颗粒提供。通常地，所述研磨颗粒悬浮在抛光流体(被称为浆料)中，或嵌在抛光垫(被称为固定研磨抛光垫)中。
当研磨颗粒悬浮于抛光流体(浆料)中时，通常是使用非研磨抛光垫将研磨颗粒运送到基板的材料层，在基板的材料层处所述研磨颗粒提供与基板的表面的机械动作，且在一些实施例中，提供化学反应。与上述相反，利用固定研磨抛光垫，研磨颗粒通常通过将它们嵌在诸如环氧树脂之类的支撑材料(例如，所述支撑材料经常被称作粘合剂材料)中而整合到抛光垫中。通常，在CMP工艺期间，所述粘合剂材料将所述研磨颗粒固定地保持在抛光垫表面的一位置处，在所述位置处，所述研磨颗粒在CMP工艺期间提供机械抛光作用给所述基板的材料层，并且有时提供与基板的材料层的化学反应。
通常地，固定研磨抛光垫在抛光性能的某些方面上比标准(非固定研磨抛光垫)优越，诸如，在具有高特征密度的区域中，平坦表面的非期望侵蚀较少，并且在诸如沟槽、接触件和线之类的凹陷特征中，膜材料的上表面非期望的碟形化(dishing)较少。然而，固定研磨抛光垫倾向有较短的寿命(每个垫几次抛光)，在从基板表面移除膜的速率方面，基板至基板间的稳定性不佳，并且在跨基板的膜移除的均匀度方面，基板至基板间的稳定性不佳。
通常，固定研磨调节盘(诸如金刚石调节盘)与标准的抛光垫一起被使用，以使抛光垫表面复原(rejuvenate)和平坦化，并且因此维持基板至基板间的稳定性抛光性能。然而，固定研磨调节盘通常与和固定研磨抛光垫一起使用不兼容，因为所述盘将从其中嵌有研磨材料的支撑环氧树脂材料的固有脆性表面移除嵌入的研磨颗粒。这样的非期望地移除研磨颗粒使得垫表面缺乏(或几乎缺乏)高效CMP工艺所必需的研磨颗粒。
因此，本技术中需要一种抛光垫以及制造抛光垫的方法，所述抛光垫具有与外部调节(诸如利用固定研磨调节盘)兼容的固定研磨抛光垫的期望的抛光特性。
发明内容
本文的实施例总体上涉及整合研磨(IA)抛光垫以及形成所述整合研磨抛光垫的方法，所述整合研磨抛光垫包括研磨颗粒，所述研磨颗粒设置在所述抛光垫的部分的抛光材料中且与所述抛光垫的部分的抛光材料化学结合。具体地，本文的实施例中，可固化树脂前驱物混合物形成有研磨颗粒，所述研磨颗粒具有可聚合基团，所述可聚合基团化学结合至所述研磨颗粒的表面。所述可固化树脂前驱物混合物用在增材(additive)制造工艺中(伴随可固化树脂子抛光材料前驱物组成物)，以形成抛光垫。在一些实施例中，所述抛光垫具有分立的(discrete)抛光元件，所述抛光元件具有研磨颗粒，所述研磨颗粒设置在所述抛光元件的抛光垫材料中，且与所述抛光元件的抛光垫材料化学结合。
在一个实施例中，一种形成抛光制品的方法包括：分配第一前驱物的第一多个液滴；以及固化所述第一多个液滴以形成第一层，所述第一层包括子抛光元件的一部分。所述方法进一步包括将所述第一前驱物和第二前驱物的第二多个液滴分配至所述第一层上，并且固化所述第二多个液滴，以形成第二层，所述第二层包括所述子抛光元件的部分和多个抛光元件的部分。在此，所述第二前驱物包括官能化的研磨颗粒，所述官能化的研磨颗粒具有化学结合至所述官能化的研磨颗粒的表面的可聚合基团。
在另一实施例中，一种形成抛光制品的方法包括：从第一前驱物的第一多个液滴形成子抛光元件；以及通过分配第二前驱物的第二多个液滴来形成多个抛光元件，所述多个抛光元件设置在所述子抛光元件中且从所述子抛光元件延伸。在此，所述第二前驱物包括经处理的金属氧化物纳米颗粒，所述经处理的金属氧化物纳米颗粒具有可聚合化合物，所述可聚合化合物结合至所述金属氧化物纳米颗粒的表面上的少于约50％的结合位点(bonding site)。所述经处理的金属氧化物纳米颗粒包括金属氧化物纳米颗粒与下述化合物的反应产物：硅烷化合物、氰酸酯化合物、磺酸化合物、磷酸化合物、羧酸化合物、或上述化合物的组合。
在另一实施例中，一种抛光制品包括：子抛光元件，所述子抛光元件包括第一前驱物混合物的第一反应产物；以及多个抛光元件，所述多个抛光元件从所述子抛光元件延伸。在此，所述多个抛光元件包括第二前驱物混合物的第二反应产物，其中所述第二前驱物混合物包括官能化的研磨颗粒。
附图说明
通过参考其中一些在附图中所示的实施例，可得到对上文简要总结的本公开内容的更具体的描述，如此能够详细了解本公开内容的上述特征。然而，应注意，附图仅示出本公开内容的典型实施例，因此不应将附图视为限制本公开内容的范围，因为本公开内容可以允许其他等效实施例。
图1A至图1D示出根据本文所阐述的方法形成的表面官能化的二氧化铈颗粒的各种性质。
图2A是使用根据本文所公开的实施例形成的整合研磨(IA)抛光垫的抛光系统的示意性剖面图。
图2B至图2C是根据本文所述的实施例的IA抛光垫的示意性透视剖面图。
图3A是根据一个实施例的用于形成整合研磨(IA)抛光垫的增材制造系统的示意性剖面图，所述抛光垫诸如为图2B至图2C中所述的IA抛光垫。
图3B和图3C示出使用图3A中描述的增材制造系统的固化工艺。
图4A至图4B示出根据一个实施例的由包括表面官能化的研磨颗粒的前驱物形成的层的性质。
图5是根据一个实施例的示出形成抛光垫的方法的流程图，所述抛光垫诸如为图2A至图2B中所述的整合研磨(IA)抛光垫。
图6是根据另一个实施例的整合研磨(IA)抛光垫的示意性俯视图。
为促进理解，已尽可能使用相同的附图标记来指定各图共通的相同元件。应考虑到，在一个实施例中所公开的元件可有利地用在其他实施例上，而无需详细叙述。
具体实施方式
本文描述的实施例总体上涉及抛光制品以及用于制造抛光工艺中所使用的抛光制品的方法。更具体地，本文所述的实施例涉及整合研磨(IA)抛光垫，以及制造IA抛光垫的方法，所述IA抛光垫具有固定研磨抛光垫的有利抛光特性，且还允许以固定研磨调节器(诸如金刚石调节器)进行调节。调节IA抛光垫的能力实现一种抛光工艺，所述抛光工艺使用非研磨抛光流体，且还具有稳定且受控的抛光性能以及延长的抛光垫寿命。
在本文中，被描述为抛光垫的抛光制品以及形成所述抛光制品的方法可应用至其它的抛光应用，包括例如磨光(buffing)。此外，尽管本文中的讨论涉及化学机械抛光(CMP)工艺，但所述制品和方法也可应用于使用化学活性的和非化学活性的抛光流体两者的其他抛光工艺。此外，本文所述的实施例可以用在至少以下产业：航空、陶瓷、硬盘驱动(HDD)、MEMS和纳米技术、金属加工、光学和电光学制造、和半导体器件制造等。
本公开内容的实施例提供整合研磨(IA)抛光垫，所述整合研磨(IA)抛光垫至少部分使用在增材制造工艺中的表面官能化的研磨颗粒来制造，所述增材制造工艺诸如是二维2D或三维3D喷墨打印工艺。增材制造工艺(诸如本文所述的三维打印(“3D打印”)工艺)能够形成具有分立(discrete)抛光区域和/或抛光特征(抛光元件)的聚合物IA抛光垫，所述抛光区域和/或特征(抛光元件)具有独特的性质及属性。通常，抛光元件的聚合物与相邻的抛光元件的聚合物在它们的界面处形成化学键，例如共价键或者离子键。因为所述抛光元件通过化学结合而与相邻的抛光元件链接，所以所述界面比起使用其他方法(诸如利用粘附层或通过热结合)附连的有分立元件的抛光垫更强且更牢固，以允许在期望时使用更剧烈的抛光或调节工艺。
在本文中，研磨颗粒是指羟基封端的金属氧化物纳米颗粒，例如单成分或多成分的金属氧化物纳米颗粒，例如，二氧化铈、氧化铝、二氧化硅、二氧化硅/氧化铝氧化物、或者上述材料的组合。在其他实施例中，所述研磨颗粒包括以羟基、硫醇基、羧酸基、氨基、或上述基团的组合来封端的金属氧化物纳米颗粒。表面官能化的研磨颗粒是指，包括化学结合至此研磨颗粒的表面上的结合位点的至少一个可聚合基团的研磨颗粒。结合位点是指，能够与本文所述的化合物反应从而与可聚合基团形成共价键的位点。
在一些实施例中，获得表面官能化的研磨颗粒的表面改性包括，使羟基封端的研磨颗粒的表面与表面改性有机化合物反应，所述表面改性有机化合物诸如为有机硅烷化合物、磺酸化合物、有机磷酸化合物、羧酸化合物、上述化合物的衍生物或上述化合物的组合。在本文所述的实施例中，羟基封端的研磨颗粒的反应产物包括具有以烯烃和羟基两者封端的表面的研磨颗粒，在下文中，这类研磨颗粒被称为烯烃封端的研磨颗粒。在其他实施例中，可利用任何可聚合基团来封端所述表面，所述可聚合基团诸如为环氧基团，例如环氧醛基团或环氧酮基团。
在一个实施例中，表面官能化的研磨颗粒是通过使研磨颗粒的表面与硅烷化合物反应而形成的，所述硅烷化合物诸如为烷氧基硅烷，诸如三氯(苯基)硅烷、三氯(己基)硅烷、三氯(十八烷基)硅烷、三甲氧基(7-辛烯-1-基)硅烷、三氯[2-(氯甲基)烯丙基]硅烷、乙烯基三甲氧基硅烷、氯(二甲基)乙烯基硅烷、烯丙基三甲氧基硅烷、丙烯酰氯、乙烯基三甲氧基硅烷、或它们的组合。研磨颗粒硅烷化合物反应用于将期望的可聚合基团接枝到研磨颗粒的羟基封端的表面上(即，如下文所示的圆形元件)，如化学反应(A)和(B)中所呈现的，其中R是甲基(CH3)。
Figure BDA0002380741520000061
在另一实施例中，表面官能化的研磨颗粒是通过使研磨颗粒的表面与氰酸酯化合物反应而形成的，所述氰酸酯化合物是诸如基于异氰酸酯的单体，诸如三-[3-(三甲氧基甲硅烷基)丙基]异氰脲酸酯或2-(甲基丙烯酰氧基)乙基异氰酸酯。例如，2-(甲基丙烯酰氧基)乙基异氰酸酯的异氰酸酯基团与羟基反应，并且形成酰胺键，造成丙烯酸基团与研磨纳米颗粒的共价结合，如化学反应(C)中所呈现的，其中R代表氢(H)或甲基(CH3)。
Figure BDA0002380741520000062
在另一个实施例中，表面官能化的研磨颗粒是通过使研磨颗粒的表面与磺酸或磷酸衍生物反应而形成的，所述磺酸或磷酸衍生物诸如是2-丙烯酰胺基-2-甲基-1-丙磺酸(如反应(D)中所示)或乙烯基膦酸酯(如反应(E)中所示)，其中R代表氢(H)或甲基(CH3)。
Figure BDA0002380741520000071
在另一个实施例中，表面官能化的研磨颗粒是通过使研磨颗粒的表面与包括丙烯酸基团的羧酸反应而形成的，诸如化学反应(F)中所示，其中R表示氢(H)或甲基(CH3)，且n为从1至50。在一些实施例中，通过使用亚硫酰氯(thionyl chloride)将含丙烯酸基团的丙烯酸转换为氯酸，而增加羧基的反应性。
Figure BDA0002380741520000072
图1A至图1D示出根据一个实施例形成的表面官能化的二氧化铈颗粒的各种性质。除了其他CMP应用以外，二氧化铈常用作用于浅沟槽隔离(STI)抛光应用的研磨颗粒，这是因为相较于氮化硅材料，二氧化铈的羟基封端表面对氧化硅(SiO2)材料呈现高亲合力，而导致在两个膜之间的所期望地高的选择性。虽然不希望受特定理论所限制，但相信二氧化铈颗粒的表面与可聚合基团的过量负载(结合位点的百分比)将非期望地影响二氧化铈颗粒与SiO2的H封端表面的反应，这影响到抛光速率以及选择性性能。因此，期望限制二氧化铈颗粒的表面上的官能化的表面位点的负载，以使得有充足的羟基封端的位点保持与SiO2的H封端的表面反应。在本文中，期望具有可聚合基团的研磨颗粒表面(诸如二氧化铈表面)的负载维持在约0.1％至约50％之间，诸如约1％至约25％之间，诸如约1％至约10％之间，诸如在约1％至约5％之间，例如，在约2％至约5％之间，或者其中研磨颗粒表面中的至少一些被表面官能化了不超过约5％。
在图1A至图1D中，通过使羟基封端的表面位点与氯(二甲基)乙烯基硅烷反应，而使二氧化铈颗粒被表面官能化，如反应(G)中所示。
Figure BDA0002380741520000081
所述反应是通过下述方式执行的：使二氧化铈颗粒与非水性的溶剂(诸如甲苯)混合，同时使用探针超声器在60℃下搅拌混合物。在超声处理期间，将氯(二甲基)乙烯基硅烷一滴接着一滴(drop by drop)添加至混合物中，并且随后将所述混合物维持在60℃达约3小时，从而完成反应，并且提供表面官能化的二氧化铈颗粒。所述表面官能化的二氧化铈颗粒通过过滤、离心、和用甲苯清洗的组合来进行纯化，以移除未反应的氯(二甲基)乙烯基硅烷。利用热重分析(TGA)、傅立叶变换红外光谱(FTIR)、透射电子显微镜(TEM)、和能量色散X射线(EDX)分析来表征(characterize)经处理的二氧化铈颗粒，以确认所述经处理的二氧化铈颗粒的官能化。
图1A示出经处理的二氧化铈颗粒的样本的热重分析(TGA)的结果。当经处理的二氧化铈颗粒107的样本从环境温度被加热到100℃(第一范围103)时，所述经处理的二氧化铈颗粒经受快速的重量损失，这可归因于从纯化工艺中留下的残留甲苯的蒸发。从100℃到800℃(特别是400℃到800℃)的第二温度范围105示出经处理的二氧化铈颗粒的样本的重量有更为逐步的下降，这可归因于结合至所述经处理的二氧化铈颗粒的表面上的结合位点的可聚合基团的碳氢化合物的点燃。图1B示出经处理的二氧化铈颗粒107与未经处理的二氧化铈颗粒111相比较的FTIR分析的结果。在约1620cm-1的波长下的CH＝CH2振动119以及在约2919cm-1和2850cm-1处的甲基反对称的和对称的振动117指示了，与未处理的二氧化铈颗粒111相比较，经处理的二氧化铈颗粒107成功地用二甲基乙烯基硅烷基团进行表面改性(并且因此成功地表面官能化)。在约3400cm-1处的OH振动115指示了，与未处理的二氧化铈颗粒111相比较，在经处理的二氧化铈颗粒107上的羟基的一部分已在反应期间被消耗掉，且进一步地指示了，经处理的二氧化铈颗粒107成功地用二甲基乙烯基硅烷基团进行表面官能化。然而，如OH振动115所示，羟基的至少一部分保持结合至经处理的二氧化铈颗粒107的表面的结合位点，因此在二氧化铈颗粒上留下足够的羟基封端的位点，在CMP工艺期间(诸如在STI抛光工艺期间)维持期望的抛光速率和/或选择性性能，其中二氧化铈颗粒的羟基封端的位点与H封端的SiO2表面反应。
图1C示出TEM图像120和130，其中经处理的二氧化铈颗粒107的滴涂布膜是通过溶剂蒸发而形成在碳涂布的铜研磨物(grind)上。如图像120和130中所示，单独的经处理的二氧化铈颗粒具有相当均匀的平均直径，所述相当均匀的平均直径介于20nm至约50nm。然而，并非出乎意料地，单独的颗粒形成较大的颗粒凝聚体，在典型的配方中，需要磨碾所述较大的颗粒凝聚体，这意味着在调配用于形成本文中所述的IA抛光垫的前驱物混合物之前或期间，会需要将较大的颗粒凝聚体分离成较小的凝聚体和/或单独的颗粒。图1D示出图像145中所示的经处理的二氧化铈颗粒的所选EDX光谱，其中Ce、O、和Si信号可归因于二氧化铈颗粒以及结合的二甲基乙烯基硅烷基团，这指示经处理的二氧化铈颗粒的表面以可聚合的二甲基乙烯基硅烷基团成功地官能化。在另一个实施例中，使用气相反应工艺(诸如流体化床)来使研磨颗粒的表面与表面改性化合物反应。
图2A是示例抛光系统250的示意性剖面图，所述示例抛光系统250使用根据本文所述的实施例而形成的IA抛光垫200。通常，使用设置在IA抛光垫200与工作台252之间的粘附剂(例如压力敏感粘附剂)将IA抛光垫200固定至抛光系统250的工作台252。基板载具258面向工作台252和安装在所述工作台252上的IA抛光垫200，所述基板载具258具有柔性隔膜(diaphragm)261，所述柔性隔膜被配置成在推动基板260的材料表面抵靠IA抛光垫200的抛光表面的同时，对基板260的不同区域施加不同的压力。所述基板载具258包括围绕基板260的载具环259。在抛光期间，载具环259上的下压力(downforce)推动载具环259抵靠IA抛光垫200，从而防止基板260从基板载具258滑动。在柔性隔膜261推动基板260抵靠IA抛光垫200的抛光表面的同时，所述基板载具258绕载具轴264旋转。工作台252绕工作台轴254以与基板载具258的旋转方向相反的方向旋转，同时基板载具258从工作台252的内直径至工作台252的外直径来回扫掠，从而部分地减少IA抛光垫200的不均等的磨耗。在本文中，工作台252和IA抛光垫200所具有的表面积大于基板260的表面积，然而在一些抛光系统中，IA抛光垫200所具有的表面积小于基板260的表面积。
在抛光期间，通过定位在工作台252之上的流体分配器268将流体226引至IA抛光垫200。通常，流体226是水、抛光流体、抛光浆料、清洁流体、或它们的组合。在本文中，所述抛光流体含有pH调整剂和/或化学活性成分(诸如氧化剂)，以实现基板260的材料表面的化学机械抛光。
通常，抛光系统250包括垫调节组件270，所述垫调节组件270包括调节器278，诸如固定研磨调节器，例如金刚石调节器。所述调节器278耦接到调节臂272，所述调节臂272具有致动器276，所述致动器276使调节器278绕其中心轴旋转。在抛光基板260之前、期间和/或之后，当调节器278扫过IA抛光垫200时，将下压力施加至调节器278。通过从IA抛光垫200的抛光表面移除抛光副产物或其他碎屑，调节器278磨损和复原(rejuvenate)IA抛光垫200和/或清洁IA抛光垫200。
图2B至图2C是根据本文所述的实施例的IA抛光垫200b-c的示意性透视剖面图。IA抛光垫200b-c可用作图2A的抛光系统250中的IA抛光垫200。在图2B中，IA抛光垫200b包括多个抛光元件204b，所述多个抛光元件204b设置在子抛光元件206b内，且从子抛光元件206b的表面延伸。多个抛光元件204b具有厚度215，子抛光元件206b具有子厚度212。如图2B和图2C所示，所述抛光元件204b、204c由子抛光元件206b、206c的一部分(例如，在区域212A内的部分)来支撑。因此，当在处理期间由基板将负载施加到IA抛光垫200b-c的抛光表面201(例如，顶表面)时，所述负载将通过抛光元件204b、204c以及子抛光元件206b、206c的部分212A来传输。在本文中，多个抛光元件204b包括柱205以及多个同心环207，所述柱205设置在IA抛光垫200b的中心中，所述多个同心环207绕柱205设置，且从所述柱205径向向外延伸。所述多个抛光元件204b和所述子抛光元件206b界定多个通道218，所述多个通道218设置在IA抛光垫200b中，位于抛光元件204b中的每一个之间且在IA抛光垫200b的抛光表面的平面与子抛光元件206b的表面之间。多个通道218使流体266(诸如抛光流体)能够分布遍及IA抛光垫200b上，且分布至IA抛光垫200b与基板260的材料表面之间的界面。在其他实施例中，抛光元件204b的图案为矩形、螺旋形、碎形(fractal)、随机(random)、其他图案、或它们的组合。在本文中，(多个)抛光元件204b-c的宽度214介于约250微米至约5毫米之间，诸如介于约250微米至约2毫米之间。(多个)抛光元件204b之间的间距(pitch)216介于约0.5毫米至约5毫米之间。在一些实施例中，宽度214和/或间距216跨IA抛光垫200b的半径而变化，以界定垫材料性质和/或研磨颗粒浓度的区域。
在图2C中，将抛光元件204c示为从子抛光元件206c延伸的圆形柱。在其他实施例中，所述抛光元件204b具有任何合适的剖面形状，例如具有环形、部分环形(例如，弧形)、椭圆形、正方形、矩形、三角形、多边形、不规则形状或上述形状的组合的柱。在一些实施例中，所述抛光元件204c的形状和宽度214以及所述抛光元件204c之间的距离跨IA抛光垫200c而变化，以调整整个IA抛光垫200c的硬度、机械强度、流体运送特性、或其他的期望性质。
在本文中，抛光元件204b-c和子抛光元件206b-c各自包括垫材料组成物，所述垫材料组成物具有低聚(oligomeric)和/或聚合(polymeric)的片段、化合物、或材料中的至少一者，所述低聚和/或聚合的片段、化合物、或材料选自由以下项组成的群组：聚酰胺、聚碳酸酯、聚酯、聚醚酮、聚醚、聚甲醛、聚醚砜、聚醚酰亚胺、聚酰亚胺、聚烯烃、聚硅氧烷、聚砜、聚苯(polyphenylene)、聚苯硫醚、聚氨酯、聚苯乙烯、聚丙烯腈、聚丙烯酸酯、聚甲基丙烯酸甲酯、聚氨酯丙烯酸酯、聚酯丙烯酸酯、聚醚丙烯酸酯、环氧丙烯酸酯、聚碳酸酯、聚酯、三聚氰胺、聚砜、聚乙烯材料、丙烯腈丁二烯苯乙烯(ABS)、卤化聚合物、嵌段共聚物以及上述项的随机共聚物，以及上述项的组合。
在一些实施例中，用于形成IA抛光垫200b-c的部分(诸如第一抛光元件204b-c和子抛光元件206b-c)的材料将包括至少一种可喷墨的预聚物组成物的反应产物，所述预聚物组成物是官能性聚合物、官能性低聚物、反应性稀释剂和固化剂的混合物，以实现IA抛光垫200b-c的期望的性质。总体上，可将所沉积的材料暴露于热或电磁辐射，所述热或电磁辐射可包括紫外线辐射(UV)、γ辐射、X射线辐射、可见辐射、IR辐射和微波辐射，且被加速的电子及离子束也可用于引发聚合反应。为了本公开内容的目的，我们不限制固化的方法或用于辅助聚合的添加剂的使用，所述添加剂诸如为敏化剂、引发剂和/或固化剂，诸如通过固化剂或氧抑制剂。在一个实施例中，从依序沉积及后沉积处理形成单一垫主体内的两个或更多个抛光元件，诸如抛光元件204b-c和子抛光元件206b-c，所述两个或更多个抛光元件包括至少一个可辐射固化的树脂前驱物组成物的反应产物，其中所述等成物含有拥有不饱和化学部分(chemical moiety)或基团的官能性聚合物、官能性低聚物、单体和/或反应性稀释剂，包括但不限于：乙烯基、丙烯酸基、甲基丙烯酸基、烯丙基和乙炔基。在抛光元件204b-c和子抛光元件206b-c内所找到的材料的硬度和/或储存模数E'不同，从而使得抛光元件204b-c的硬度和/或储存模数E'的值大于子抛光元件206b-c。在一些实施例中，抛光元件204b-c的材料组成和/或材料特性在抛光元件到抛光元件之间不同。单独化的材料组成和/或材料特性允许了针对特定需求修饰抛光垫的性质。
所述多个抛光元件204b-c中的一个或多者的至少一部分包括设置在所述多个抛光元件204b-c的抛光垫材料组合物中的研磨颗粒，且所述研磨颗粒共价地或离子地化学结合至所述多个抛光元件204b-c的抛光垫材料组成物。在本文中，抛光元件204b-c至少包括可辐射固化的树脂前驱物组成物与表面官能化的研磨颗粒的反应产物，所述组成物含有具有不饱和化学部分或基团的官能性聚合物、官能性低聚物、单体、或反应性稀释剂，所述不饱和化学部分或基团包括但不限于：乙烯基、丙烯酸基、甲基丙烯酸基、烯丙基、和乙炔基，而所述表面官能化的研磨颗粒诸如为烯烃封端的研磨颗粒，例如烯烃封端的金属氧化物纳米颗粒。通常，研磨颗粒的浓度小于抛光元件204b的抛光垫材料组成物的约70重量％，诸如小于约50重量％、诸如介于约1重量％至约50重量％之间、介于约1重量％至约40重量％之间、介于约1重量％至约30重量％之间、介于约1重量％至约20重量％之间、介于约1重量％至约10重量％之间，例如，介于约1重量％至约5重量％之间。在本文中，表面官能化的研磨颗粒均匀地分布在整个抛光元件204b-c上。
在其他实施例中，表面官能化的研磨颗粒均匀地分布在从子抛光元件206b-c的表面延伸的抛光元件204b-c的部分中，并且在抛光垫材料中于子抛光元件206b-c的表面下方延伸的抛光元件204b-c的部分中不包括所述表面官能化的研磨颗粒。在其他实施例中，研磨颗粒的浓度从抛光元件204b-c的第一端到抛光元件204b-c的第二端(所述第二端远离所述第一端)增加或减少，其中第二端形成IA抛光垫200b-c的抛光表面。在其他实施例中，所述研磨颗粒设置在抛光元件的研磨层中，其中垫材料(非研磨层)不包括设置在所述垫材料层(非研磨层)之间的研磨颗粒或较低浓度的研磨颗粒。在一些实施例中，IA抛光垫200b-c进一步包括设置在子抛光元件206b-c的抛光垫材料组成物中的研磨颗粒，并且所述研磨颗粒化学结合到所述子抛光元件206b-c的抛光垫材料组成物。
可使用本文所述的方法和材料组成来进行调整的典型抛光垫材料组成物性质包括：储存模数E’、损耗模数E”、硬度、tanδ、屈服强度、极限拉伸强度、伸长率、导热率、ζ电位、质量密度、表面张力、泊松比、断裂韧性、表面粗糙度(Ra)、玻璃转变温度(Tg)和其他相关的性质。例如，储存模数E’影响抛光结果，诸如从基板的材料层表面移除的速率和所得到的均匀度。通常，具有中等或高的储存模数E’的抛光垫材料组成物为用于PMD、ILD、和STI的介电膜提供较高的移除速率，并且导致在凹陷特征(诸如沟槽、接触件、和线)中的膜材料的上表面有较少的非期望的碟形化。具有低储存模数E’的抛光垫材料组成物通常在抛光垫的寿命上提供更为稳定的移除速率，在具有高特征密度的区域中引起较少的非期望的平坦表面腐蚀，并且导致材料表面的微刮擦减少。总体而言，有低储存模数的抛光垫材料组成物不适合作为用于常规的固定研磨抛光垫的研磨颗粒的粘合剂材料，因为比起硬的、高储存模数E’的常规环氧树脂类型的支撑材料，研磨颗粒可更容易地逃离较软的垫材料。在表1中总结了在30℃(E’30)和90℃(E’90)的温度下的低、中、或高储存模数E’的垫材料组成物的表征：
表1
低储存模数组成物 中储存模数组成物 高储存模数组成物
E’30 5MPa-100MPa 100MPa-500MPa 500MPa-3000MPa
E’90 <17MPa <83MPa <500MPa
通常，子抛光元件206b-c由与形成抛光元件204b-c的材料不同的材料形成，诸如具有低(软)或中等的储存模数E’的材料。所述抛光元件204b-c通常是由具有中或高(硬)的储存模数E’的材料形成。利用标准的非研磨抛光垫和浆料工艺，中或高的储存模数的抛光材料通常是必需的，以用于在抛光诸如SiO2之类的介电材料时维持期望的材料移除速率。这是因为，相较于较软的垫，较硬的垫材料更有效地将松散的研磨颗粒保持或支撑抵靠基板的材料表面，从而允许当下压力推动基板抵靠抛光垫表面而使得垫材料变形时，研磨颗粒沉至垫表面下方。同样，已发现，使用软或低储存模数E’的抛光垫的CMP工艺倾向于具有非均匀的平坦化结果，这是由于，在由载具环259(图2A)所生成的施加力和在CMP工艺期间由柔性隔膜261生成的施加力下，软或低储存模数E’的抛光垫相对地容易变形。换言之，用于形成软或低储存模数E’的抛光垫的材料的柔软的、柔性的且低储存模数E’的性质允许由载具环259供应的力的效应最小化，从而改进垫补偿载具环下压力的能力。类似地，常规的固定研磨抛光垫通常利用具有高硬度值的材料，以将研磨颗粒物理地保持就位。然而，已发现使用“硬”抛光垫材料的CMP工艺倾向于具有非均匀的平坦化结果，这是由于经抛光的基板260(图2A)的边缘处所发现的边缘效应所致，详细地，所述效应与施加力给载具环259(图2A)以补偿较大的固有抛光不均匀性的需求有关，所述较大的固有抛光不均匀性在CMP工艺期间于基板边缘处发现。相信本文所述的IA抛光垫的优点之一在于，能够维持高移除速率和低侵蚀，其中抛光元件204b-c包括具有经调整的和/或受控的低或中等的储存模数E’的抛光垫材料组成物。这是因为，期望地定位的研磨颗粒将通过与所述研磨颗粒的共价结合而固定在垫表面，而不会像利用标准的软抛光垫和浆料工艺那样沉入软的垫材料中。通过将研磨颗粒固定在软的垫材料的抛光表面处，能够维持研磨颗粒与基板的材料表面之间的化学活性，诸如二氧化铈颗粒与SiO2基板表面之间的化学活性，以实现合理的材料移除速率。因此，在一些实施例中，抛光元件204b-c将具有低或中等的储存模数E’。然而，也认识到，表面官能化的研磨颗粒作为由可辐射固化的树脂前驱物组成物所形成的聚合物链之间的交联剂。在一些实施例中，作为交联剂的此功能会导致抛光元件204b-c有较高的储存模数E’，这取决于可聚合的封端的结合位点(诸如烯烃封端的结合位点)在研磨颗粒上的负载和/或可辐射固化的树脂前驱物组成物中的表面官能化的研磨颗粒的浓度。因此，在一些实施例中，期望将可聚合基团的负载(研磨颗粒的表面上的可聚合基团封端的结合位点的百分比)(诸如烯烃封端基团的负载)限制为小于约10％、诸如小于约5％，例如在2％和5％之间。
除了将研磨颗粒锚定(anchor)到抛光元件204b-c的抛光表面之外，通过将研磨颗粒化学结合至所述抛光元件204b-c的抛光材料，研磨颗粒的表面官能化也增加用于在增材制造工艺中制造抛光垫的前驱物组成物的化学兼容性，所述增材制造工艺诸如为图3A至图3C中所述的3D喷墨打印工艺。
图3A是根据本文所述的实施例的用于形成IA抛光垫(诸如IA抛光垫200b-c)的增材制造系统350的示意性剖面图。在本文中，所述增材制造系统350具有第一打印机360和第二打印机370，以通过一个或多个分配喷嘴335来分配第一前驱物组成物359和第二前驱物组成物369的液滴。所述打印机360、370在打印工艺期间彼此独立地移动、且独立于制造支撑件302移动，从而使得在制造支撑件302上的所选位置处能够放置前驱物组成物359和369的液滴，以形成抛光垫，诸如IA抛光垫200b-c。所选位置共同存储为CAD兼容的打印图案，所述CAD兼容的打印图案可由电子控制器305读取，所述电子控制器305引导制造支撑件302的运动、打印机360、370的运动、以及从喷嘴335输送液滴。
通常，所述第一前驱物组成物359用于形成子抛光元件206b-c，而所述第二前驱物组成物369则用于形成图2B至图2C中所示的IA抛光垫200b-c的多个抛光元件204b、204c。在本文中，第一前驱物组成物359和第二前驱物组成物369各自包括至少为单官能性的官能性聚合物、官能性低聚物、单体和/或反应性稀释剂的一个或多个的混合物，并且当暴露于自由基、路易斯酸(Lewis acid)、和/或电磁辐射时历经聚合。在一些实施例中，所述第一前驱物组成物359和/或第二前驱物组成物369进一步包括一种或多种光引发剂。
在本文所述的实施例中，第二前驱物组成物369进一步包括表面官能化的研磨颗粒，诸如表面官能化的二氧化铈颗粒、表面官能化的氧化铝颗粒、表面官能化的二氧化硅颗粒、表面官能化的二氧化硅/氧化铝氧化物颗粒、或上述项的组合，以及一种或多种分散剂和/或悬浮剂。除了能够将研磨颗粒化学结合至本文所述的抛光元件的抛光垫材料之外，研磨颗粒的表面官能化的增加了所述研磨颗粒与典型有机液体树脂前驱物组成物的兼容性。此增加的兼容性是因为将研磨颗粒的至少一部分亲水性羟基表面封端位点转化为疏水性可聚合有机基团。此增加的兼容性使得本文所述的表面官能化的研磨颗粒能够进入包括液体前驱物组成物的悬浮液，并且保持悬浮在所述悬浮液中，并且形成高度稳定且均质的悬浮液。
此外，使研磨颗粒的表面官能化期望地提高了前驱物组成物悬浮液的热稳定性和/或化学兼容性。虽然不希望受任何特定理论所限制，但相信未改性的研磨颗粒充当在前驱物组成物内的至少一部分成分的聚合催化剂(通过在典型分配温度下引发热固化反应)。这种过早(premature)聚合非期望地增加前驱物组成物的粘度，从而在分配所述前驱物组成物的液滴时产生诸如喷嘴堵塞之类的难题。包括表面官能化的研磨颗粒的前驱物组成物具有少如少于约5％的研磨颗粒与可聚合基团结合的结合位点(诸如介于约2％至约5％之间)，这样的前驱物组成物相较于包括未处理的研磨颗粒的前驱物组成物，具有增加的热稳定性和/或化学兼容性(即，通过打印机喷嘴分配的粘度得到改进)。
在本文中，至少第二前驱物组成物369中的表面官能化的研磨颗粒的浓度期望地维持在以重量计约1％至约50％之间，诸如在约1重量％至约40重量％之间、约1重量％至约30重量％之间、约1重量％至约20重量％之间、约1重量％至约10重量％之间、或约1重量％至约5重量％之间，例如小于约10重量％，或小于约5重量％。在其他实施例中，表面官能化的研磨物占第一前驱物组成物359的不到约70重量％。在其他实施例中，表面官能化的研磨颗粒和未改性的研磨颗粒占第一前驱物组成物359的不到约70重量％。
在本文中，官能性聚合物的示例包括多官能性丙烯酸酯，包括二官能、三官能、四官能和更高官能性的丙烯酸酯，诸如1,3,5-三丙烯酰基六氢-1,3,5-三嗪或三羟甲基丙烷三丙烯酸酯。
官能性低聚物包括单官能性和多官能性低聚物、丙烯酸酯低聚物，诸如脂肪族聚氨酯丙烯酸酯低聚物、脂肪族六官能性聚氨酯丙烯酸酯低聚物、二丙烯酸酯、脂肪族六官能性丙烯酸酯低聚物、多官能性聚氨酯丙烯酸酯低聚物、脂肪族聚氨酯二丙烯酸酯低聚物、脂肪族聚氨酯丙烯酸酯低聚物、脂肪族聚酯聚氨酯二丙烯酸酯掺混脂肪族二丙烯酸酯低聚物、或上述项组合，例如双酚-A乙氧基化二丙烯酸酯、或聚丁二烯二丙烯酸酯。在一个实施例中，所述官能性低聚物包括可从美国乔治亚州Alpharetta的Allnex公司购得的四官能性丙烯酸酯化聚酯低聚物
Figure BDA0002380741520000173
且所述官能性低聚物包括可从美国宾夕法尼亚州Exton的Sartomer USA公司购得的基于脂肪族聚酯的聚氨酯二丙烯酸酯低聚物(CN991)。
单体包括单官能性单体和多官能性单体。单官能性单体包括：丙烯酸四氢呋喃酯(例如SR285，来自
Figure BDA0002380741520000172
)、甲基丙烯酸四氢呋喃酯、乙烯基己内酰胺、丙烯酸异冰片酯、甲基丙烯酸异冰片酯、丙烯酸2-苯氧基乙酯、甲基丙烯酸2-苯氧基乙酯、丙烯酸2-(2-乙氧基乙氧基)乙酯、丙烯酸异辛酯、丙烯酸异癸酯、甲基丙烯酸异癸酯、丙烯酸十二酯、甲基丙烯酸十二酯、丙烯酸十八酯、甲基丙烯酸十八酯、环三羟甲基丙烷甲缩醛丙烯酸酯(cyclic trimethylolpropane formal acrylate)、2-[[(丁氨基)羰基]氧基]丙烯酸乙酯(例如，来自RAHN USA公司的Genomer 1122)、3,3,5-三甲基环己烷丙烯酸酯、或单官能性甲氧基化PEG(350)丙烯酸酯。多官能性单体包括二醇的二丙烯酸酯或二甲基丙烯酸酯和聚醚二醇，诸如丙烯酸化的二丙烯酸新戊二醇酯、二丙烯酸1,6-己二醇酯、二甲基丙烯酸1,6-己二醇酯、二丙烯酸1,3-丁二醇酯、二甲基丙烯酸1,3-丁二醇酯、二丙烯酸1,4-丁二醇酯、二甲基丙烯酸1,4-丁二醇酯、烷氧基化脂肪族二丙烯酸酯(例如，来自
Figure BDA0002380741520000181
的SR9209A)、二丙烯酸二乙二醇酯、二甲基丙烯酸二乙二醇酯、二丙烯酸二丙二醇酯、二丙烯酸三丙二醇酯、二甲基丙烯酸三乙二醇酯、烷氧基化二丙烯酸己二醇酯、或上述项的组合，例如来自
Figure BDA0002380741520000182
的SR562、SR563、SR564。
反应性稀释剂包括单丙烯酸酯、丙烯酸2-乙基己酯、丙烯酸辛基癸酯、环三羟甲基丙烷甲缩醛丙烯酸酯、丙烯酸己内酯、丙烯酸异冰片酯(IBOA)、或烷氧基化甲基丙烯酸十二酯。
本文使用的光衣引发剂包括聚合光引发剂(polymeric photoinitiator)和/或低聚光引发剂(oligomer photoinitiator)，诸如苯偶姻醚、芐基缩酮、乙酰基苯酚、烷基苯酮、氧化膦、二苯甲酮化合物、和噻吨酮(thioxanthone)化合物(其包括胺增效剂)、或上述项组合。例如，在一些实施例中，光引发剂包括由德国Ludwigshafen的BASF公司制造的
Figure BDA0002380741520000183
产品，诸如Irgacure 819、Irgacure 784、Irgacure 379、Irgacure 2022、Irgacure 1173、Irgacure 500、上述产品的组合、或等效组成物。
分散剂和/或悬浮剂通常用于，例如通过增加研磨颗粒之间的静电互斥(ζ电位)，从而使研磨颗粒在液体悬浮液内稳定。分散剂和/或悬浮剂能够用于使表面官能化的研磨颗粒均匀悬浮在前驱物组成物359和369的液体中。分散剂和/或悬浮剂的示例包括：
Figure BDA0002380741520000184
产品，诸如HypermerKD4及Hyper KD57，可购自美国特拉华州的New Castle的Croda公司；或是BYK Dis2008、BYK JET-9151、或BYK JET-9152，可购自德国的BYK-Gardner股份有限公司。
通常，由打印机360、370来分配的前驱物组成物359和369的液滴所形成的层是通过暴露至辐射321而固化，所述辐射321来自辐射源320，诸如紫外光(UV)源、x射线源或其他类型的电磁波源。在本文中，辐射321是由UV源提供的UV辐射。在其他实施例中，前驱物组成物359和/或369通过暴露至热能而固化。
图3B示出使用图3A的增材制造系统350的固化工艺。图3B示出设置在制造支撑件302上的抛光元件的一个或多个先前形成的层346的一部分，所述抛光元件诸如为抛光元件204b-c。处理期间，打印机360和370将一种或多种前驱物组成物(诸如第二前驱物组成物369)的多个液滴343输送到一个或多个第一层346的表面346A。多个液滴343形成多个第二层348中的一个层，在图3B中，所述多个第二层348中的一个层包括固化部分348A和未固化部分348B，其中所述固化部分已经暴露于来自辐射源320的辐射321。在本文中，第一层的固化部分348A的厚度介于约0.1微米至约1毫米之间，诸如介于约5微米至约100微米之间，例如介于约25微米和约30微米之间。
图3C是分配至一个或多个先前形成的层346的表面346A上的液滴343的特写剖面图。如图3C中所示，一旦液滴343被分配到表面346A上之后，所述液滴343扩展到液滴直径343A而具有接触角α。所述液滴直径343A和接触角α是至少下述各项的函数：前驱物组成物的材料性质、一个或多个先前形成的层346的表面346A处的能量(表面能)、和时间；然而，从液滴接触所述一个或多个先前形成的层346的表面346A的时刻起，在短时间(例如小于约一秒)之后，液滴直径343A和接触角α会达到平衡状态。在一些实施例中，液滴343在达到平衡直径和接触角α之前固化。通常，所述液滴343与表面346A接触之前具有介于约10至约200微米之间的直径，诸如介于约50微米至约70微米之间，并且在与表面346A接触之后，所述液滴343扩展到约10至约500微米之间，介于约50至约200微米之间。
在本文中，前驱物组成物359和369调被配成在约25℃下具有约80cP至约110cP之间的粘度，在约70℃下具有约15cP至约30cP之间的粘度，或是对于约50℃至约150℃的温度而言介于10cP至约40cP之间，使得混合物可通过打印机360和370的分配喷嘴335有效地分配。在一些实施例中，所述第二前驱物组成物369再循环(或若不然则是机械搅拌)，以确保表面官能化的研磨颗粒维持在液体前驱物混合物中均匀地悬浮。
图4A至图4B示出由前驱物混合物形成的层的性质，所述前驱物混合物包括根据本文所述的实施例从而形成的表面官能化的研磨颗粒。图4A是其中设置有表面官能化的研磨物的抛光材料层的TEM，所述表面官能化的研磨物是使用图3A至图3C中描述的实施例由具有表2中所述的配方的前驱物来形成。在此实施例中，所述表面官能化的二氧化铈颗粒和悬浮剂在丙烯酸单体(IBOA)中混合从而形成混合物。使用探针超声器磨碾混合物，以使较大的二氧化铈颗粒的凝聚体碎裂成较小凝聚体或单独的颗粒，其平均直径在约30nm和约300nm之间。在其他实施例中，在前驱物混合之前、期间、或之后，使用其他类型的磨碾工艺(例如球磨)使将研磨颗粒的较大凝聚体减少期望的尺寸。磨碾后，将表2的其余成分添加至混合物中，从而形成前驱物组成物，通过超声处理以将所述前驱物组成物均质化，以使得表面官能化的研磨颗粒均匀地分布在所述前驱物组成物中。如图4A中的图像所示，二氧化铈粒子在打印层内具有均匀分布。图4B示出设置在由表2中所示的前驱物形成的层中的二氧化铈颗粒(在插页图像420中被示出)的EDX光谱，其中Ce、O和Si信号可归因于二氧化铈颗粒和结合的二甲基乙烯基硅烷基团，这指示成功地以可聚合的二甲基乙烯基硅烷基团将处理过的二氧化铈颗粒表面进行表面官能化。
表2
Figure BDA0002380741520000201
图5是示出根据本文所述的实施例的形成抛光垫(诸如图2A至图2B的IA抛光垫200b-c)的方法500的流程图。在活动510处，所述方法包括分配第一前驱物的第一多个液滴，所述第一前驱物诸如是图3A至图3C中描述的第一前驱物359。在本文中，所述第一前驱物包括可固化的树脂组成物，且所述第一前驱物是一种或多种官能性聚合物、官能性低聚物、单体、反应性稀释剂、或上述项的组合的混合物。在此实施例中，所述第一前驱物进一步包括一种或多种光引发剂，以使得能够使用UV辐射来固化经分配的第一多个液滴。在本文中，方法500中所使用的前驱物具有下述粘度：在约25℃下为介于约80cP至约110cP之间、在约70℃下为介于约15cP至约30cP之间、或对于约50℃和约150℃之间的温度为介于约10cP至约40cP之间，而使得来自所述前驱物的液滴能够通过打印器360的分配喷嘴335分配。
在活动520处，所述方法500包括固化第一多个液滴，以形成第一多个层中的一层，诸如图3B至图3C中所示的一个或多个先前形成的层346，在本文中的所述第一多个层中的一层包括子抛光元件的一部分，诸如IA抛光垫200b-c的子抛光元件206b-c。在本文中，第一多个液滴通过暴露至来自UV辐射源(例如辐射源320)的UV辐射而固化，所述UV辐射具有在约170nm至约500nm之间的波长。
在活动530处，所述方法500包括将第一前驱物和第二前驱物的第二多个液滴分配到第一多个层上，所述第二前驱物包括表面官能化的研磨颗粒，所述表面官能化的研磨颗粒具有化学结合到所述表面官能化的研磨颗粒的表面的至少一个可聚合基团。在本文中，所述表面官能化的研磨颗粒包括羟基封端的金属氧化物纳米粒子(诸如二氧化铈)与有机化合物的反应产物，所述有机化合物诸如为硅烷有机化合物、氰酸酯化合物、磺酸化合物、磷酸有机化合物、羧酸化合物或上述化合物的组合。在一些实施例中，所述羟基封端的金属氧化物纳米颗粒和有机化合物的反应产物形成烯烃封端的研磨颗粒。在此实施例中，负载(化学结合到可聚合化合物的表面位点的百分比)少于约50％，例如少于约50％的表面位点被烯烃封端，并且，第二前驱物中的表面官能化的研磨颗粒的浓度为介于约1重量％至约50重量％之间。在另一个实施例中，在第二前驱物中的研磨颗粒(包括非官能化的研磨颗粒)的总浓度小于约70％。
通常，所述第二前驱物包括一种或多种一种或多种官能性聚合物、官能性低聚物、单体、反应性稀释剂、或上述项的组合的混合物。在此实施例中，所述第二前驱物进一步包括光引发剂，以实现UV固化，并且包括分散剂和/或悬浮剂，以稳定第二前驱物混合物中的官能化的研磨颗粒，并将所述官能化的研磨颗粒维持在悬浮液中悬浮。此实施例中，所述表面官能化的研磨颗粒或所述表面官能化的研磨颗粒的凝聚体的平均直径为介于约10nm至约5微米之间，诸如介于约30nm至500nm之间，诸如介于约30nm至300nm之间，例如介于约100nm和约150nm之间。
在活动540处，所述方法500包括固化第二多个液滴以形成第二层，所述第二层包括子抛光元件和多个抛光元件的部分，诸如第二抛光元件204b-c。在本文中，固化所述第二多个液滴包括，将所述第二多个液滴暴露于UV辐射，从而聚合所述第二多个液滴，并在所述第二多个液滴之间的界面处形成化学键。以此方式，在包括子抛光元件的部分的聚合物材料以及在包括抛光元件的部分的聚合物材料之间，在它们的界面处形成化学键，诸如共价键和/或离子键。进一步地，所述表面官能化的研磨颗粒作为第二前驱物混合物的反应产物之间的交联剂，这是通过与所述反应产物形成化学键而达成的。
上文所述的方法与本文所述的IA抛光垫一起使用，或与其中期望将研磨颗粒化学结合至抛光垫材料的任何抛光垫一起使用。所述方法的益处包括，形成具有在CMP工艺期间、之前、或之后与金刚石的调节相容的可调整的抛光性质的IA抛光垫。其他实施例包括，通过输送含有不同前驱物的液滴以形成IA抛光垫，所述不同前驱物具有不同浓度的研磨颗粒，以使得研磨颗粒浓度可以跨抛光垫材料的表面而变化，如图6所示。
图6是与基于卷材(web)或辊对辊(roll-to-roll)型抛光系统一起使用的IA抛光垫600的示意性顶视图。所述IA抛光垫600是使用增材制造系统而形成的，诸如图3A至图3B中所示的增材制造系统350。在本文中，IA抛光垫600配置在第一辊681和第二辊682之间的抛光工作台652上。所述IA抛光垫600包括有浓度梯度的研磨颗粒，所述研磨颗粒在抛光表面608上结合至所述IA抛光垫600的抛光垫材料。在本文中，所述IA抛光垫600具有包括低浓度研磨颗粒的第一区域602、包括高浓度研磨颗粒的第二区域604、以及包括中等浓度的研磨颗粒的中间区域603。不同浓度的研磨颗粒的区域602至604是根据本文的实施例由多种前驱物组成物形成的，所述多种前驱物组成物各自包括不同浓度的表面官能化的研磨颗粒。在其他实施例中，通过交替包括高浓度研磨颗粒的前驱物组成物与包括低浓度研磨颗粒的前驱物组成物的液滴，从而形成不同浓度的区域。
虽然前述内容涉及本公开内容的实施例，但可在不背离本公开内容的基本范围的情况下设计本公开内容的其他和进一步的实施例，并且本公开内容的范围由所附权利要求来确定。

Claims (15)

1.一种形成抛光制品的方法，包括：
分配第一前驱物的第一多个液滴；
固化所述第一多个液滴以形成第一层，所述第一层包括子抛光元件的一部分；
将所述第一前驱物和第二前驱物的第二多个液滴分配至所述第一层上，所述第二前驱物包括官能化的研磨颗粒，所述官能化的颗粒具有化学结合至所述官能化的颗粒的表面的可聚合基团；和
固化所述第二多个液滴以形成第二层，所述第二层包括所述子抛光元件的部分和多个抛光元件的部分。
2.如权利要求1所述的方法，进一步包括：磨碾所述第二前驱物，以使得所述官能化的研磨颗粒或所述官能化的颗粒的组合具有介于约10nm至约300nm之间的平均直径。
3.如权利要求1所述的方法，进一步包括：分配所述第二前驱物的第三多个液滴至一个或多个第二层上；以及固化所述第三多个液滴以形成第三层，所述第三层包括所述多个抛光元件的部分。
4.如权利要求1所述的方法，其中固化所述第二多个液滴包括：在垫材料与子抛光材料的界面处将所述多个抛光元件的所述垫材料化学结合至所述子抛光元件的所述子抛光材料。
5.如权利要求4所述的方法，其中所述官能化的研磨颗粒包括金属氧化物纳米颗粒。
6.如权利要求4所述的方法，其中所述官能化的研磨颗粒的所述表面的少于约50％的结合位点具有与所述结合位点结合的所述可聚合基团。
7.如权利要求4所述的方法，其中所述官能化的研磨颗粒或所述官能化的研磨颗粒的凝聚体具有介于约10nm至约5微米之间的平均直径，并且其中所述官能化的研磨颗粒构成介于约1重量％至约50重量％之间的所述第二前驱物。
8.如权利要求7所述的方法，其中固化所述第二多个液滴包括将所述第二多个液滴暴露至UV辐射。
9.如权利要求4所述的方法，其中所述官能化的研磨颗粒包括金属氧化物纳米颗粒与以下项的反应产物：硅烷化合物、氰酸酯化合物、磺酸化合物、磷酸化合物、羧酸化合物或它们的组合。
10.一种形成抛光制品的方法，包括：
从第一前驱物的第一多个液滴形成一子抛光元件；和
通过分配第二前驱物的第二多个液滴从而形成多个抛光元件，所述多个抛光元件设置在所述子抛光元件中且从所述子抛光元件延伸，所述第二前驱物包括经处理的金属氧化物纳米颗粒，所述经处理的纳米颗粒具有可聚合化合物，所述可聚合化合物结合至所述金属氧化物纳米颗粒的表面上的少于约50％的结合位点，其中所述经处理的金属氧化物纳米颗粒包括金属氧化物纳米颗粒与以下项的反应产物：硅烷化合物、氰酸酯化合物、磺酸化合物、磷酸化合物、羧酸化合物或它们的组合。
11.一种抛光制品，包括：
子抛光元件，所述子抛光元件包括第一前驱物混合物的第一反应产物；和
多个抛光元件，所述多个抛光元件从所述子抛光元件延伸，所述多个抛光元件包括第二前驱物混合物的第二反应产物，其中所述第二前驱物混合物包括官能化的研磨颗粒。
12.如权利要求11所述的抛光制品，其中所述官能化的研磨颗粒包括金属氧化物纳米颗粒与以下项的反应产物：硅烷化合物、氰酸酯化合物、磺酸化合物、磷酸化合物、羧酸化合物或它们的组合。
13.如权利要求12所述的抛光制品，其中所述官能化的研磨颗粒或所述官能化的研磨颗粒的凝聚体具有介于约10nm至约5微米之间的平均直径。
14.如权利要求11所述的抛光制品，其中所述官能化的研磨颗粒的表面上的少于约50％的结合位点化学结合至可聚合化合物。
15.如权利要求14所述的抛光制品，其中官能化的研磨颗粒包括烯烃封端的基团。
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US20230052048A1 (en) 2023-02-16
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US20190030678A1 (en) 2019-01-31
US11471999B2 (en) 2022-10-18
TWI806884B (zh) 2023-07-01
KR20200023526A (ko) 2020-03-04
TW201930011A (zh) 2019-08-01
KR102539021B1 (ko) 2023-06-02

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