CN111320863A - 制备研磨垫之组合物 - Google Patents
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Abstract
一种用于制备研磨垫之组合物,包含:15~25重量百分比之4,4'‑亚甲基双(2‑氯苯胺)、20~40重量百分比之异氰酸酯、30~50重量百分比之多元醇以及3~10重量百分比之导电添加物。前述导电添加物包含碳黑、碳纤维、氧化铝颗粒或其混合物。前述导电添加物带有电荷。
Description
技术领域
本发明涉及一种制备研磨垫之组合物及其所制备之研磨垫。更进一步地,本发明涉及一种制备研磨垫之组合物,用于制备具有表面电荷之研磨垫以优化晶圆的化学机械研磨制程。
背景技术
化学机械研磨(Chemical mechanical polishing或Chemical mechanicalplanarization,简称CMP)为在特定的温度、压力以及化学成分中,将一半导体晶圆在一旋转的研磨平面上进行研磨的过程,或是在前述研磨平面上旋转晶圆而达到研磨的效果。前述研磨平面可以是一个由软性多孔材料(例如发泡聚氨酯)所制成的平面状的研磨垫。在CMP处理过程中,先将前述研磨平面利用一水性且具有化学活性的研磨浆进行润湿。前述研磨浆可为酸性或是碱性,一般包含研磨颗粒、活性化学成分(例如过渡金属之螯合盐类或氧化剂)、佐剂(例如溶剂、缓冲液、及/或钝化剂)。具体而言,研磨浆中的活性化学成分对晶圆进行化学蚀刻;而研磨浆中的研磨颗粒结合研磨垫对晶圆进行机械研磨。一般来说,CMP是利用调整晶圆的旋转速度以控制CMP处理的速度。例如,较高的晶圆旋转速度可以加快研磨的速度,反之亦然。然而,只透过调整晶圆的旋转速度很难精准地控制CMP处理的效能。
因此,需要提出一种可以优化CMP处理效能的化学机械研磨装置。
发明内容
有鉴于此,本发明提供一种具有表面电荷的研磨垫以优化晶圆的化学机械研磨制程。
在一实施例中,本发明提供一种用于制备研磨垫的组合物。前述组合物包含:15~25重量百分比之4,4'-亚甲基双(2-氯苯胺)、20~40重量百分比之异氰酸酯、30~50重量百分比之多元醇以及3~10重量百分比之导电添加物。前述导电添加物包含碳黑、碳纤维、氧化铝颗粒或其混合物。前述导电添加物带有电荷。
在另一实施例中,本发明提供一种用于化学机械研磨的研磨垫,由一组合物所制成。前述组合物包含:15~25重量百分比之4,4'-亚甲基双(2-氯苯胺)、20~40重量百分比之异氰酸酯、30~50重量百分比之多元醇以及3~10重量百分比之导电添加物。前述导电添加物包含碳黑、碳纤维、氧化铝颗粒或其混合物。前述导电添加物带有电荷。
在又一实施例中,本发明提供一种制备研磨垫的方法。前述方法包含步骤S401至S403。在步骤S401中,提供一种用于制备前述研磨垫的组合物。前述组合物包含:15~25重量百分比之4,4'-亚甲基双(2-氯苯胺)、20~40重量百分比之异氰酸酯、30~50重量百分比之多元醇以及3~10重量百分比之导电添加物。前述导电添加物包含碳黑、碳纤维、氧化铝颗粒或其混合物。前述导电添加物带有电荷。步骤S402中,将前述组合物放入一敞口铸型中。在步骤S403中,加热硬化前述组合物以产生一聚胺酯发泡树脂。
在又一实施例中,本发明提供一种用于研磨晶圆的化学机械研磨装置。前述化学机械研磨装置包含一研磨平台、一固定环、以及一研磨头。前述研磨平台具有一研磨垫,用于研磨前述晶圆。前述研磨垫由一组合物所制备。前述组合物包含:15~25重量百分比之4,4'-亚甲基双(2-氯苯胺)、20~40重量百分比之异氰酸酯、30~50重量百分比之多元醇以及3~10重量百分比之导电添加物。前述导电添加物包含碳黑、碳纤维、氧化铝颗粒或其混合物。前述导电添加物带有电荷。前述固定环用于固定前述晶圆。前述研磨头连接于前述固定环,用于转动前述固定环。
综上所述,本发明实施例之研磨垫由一包含氨基甲酸乙酯预聚物以及导电添加物之组合物所制备而成。前述组合物中的导电添加物带有电荷。因此,由本发明之组合物所制成的研磨垫具有表面电荷,可与晶圆表面以及研磨浆中的电荷产生静电吸引力或排斥力,以此方式可以优化研磨的效果。
附图说明
图1为本发明一实施例之一种化学机械研磨(chemical mechanical polishing,CMP)装置的示意图。
图2A与图2B为图1的化学机械研磨装置之研磨垫具有表面电荷产生的效果的示意图。
图3A与图3B为图1的研磨垫的各种实施方式。
图4为本发明另一实施例之一种制造研磨垫的方法的流程图。
主要元件符号说明
化学机械研磨装置 100
研磨平台 110
研磨垫 111
第一研磨垫 111a
第二研磨垫 111b
第三研磨垫 111c
第四研磨垫 111d
方向 112、141、142
固定环 120
研磨头 130
驱动马达 140
研磨浆供应管 151
喷嘴 152
研磨浆 153
过滤器 154
晶圆 S1
方法 S400
步骤 S401~S403
如下具体实施方式将结合上述附图进一步说明本发明。
具体实施方式
下面将结合本发明实施例中的附图,对本发明实施例中的技术方案进行清楚、完整地描述,显然,所描述的实施例仅仅是本发明一部分实施例,而不是全部的实施例。基于本发明中的实施例,本领域普通技术人员在没有做出创造性劳动前提下所获得的所有其他实施例,都属于本发明保护的范围。
除非另有定义,本文所使用的所有的技术和科学术语与属于本发明的技术领域的技术人员通常理解的含义相同。本文中在本发明的说明书中所使用的术语只是为了描述具体的实施例的目的,不是旨在于限制本发明。
下面结合附图,对本发明的一些实施方式作详细说明。在不冲突的情况下,下述的实施例及实施例中的特征可以相互组合。
请参阅图1,本发明之一实施例提供一种化学机械研磨装置100。如图1所示,前述化学机械研磨装置100包含一研磨头130以及一固定环120。前述固定环120用于固定一半导体晶圆S1。一软垫(图未示)可设置在前述固定环120与前述晶圆S1之间,且前述晶圆S1可利用部分真空或是黏着的方式紧紧贴附在前述软垫上。一驱动马达140驱动前述研磨头130持续沿一方向141转动。前述驱动马达140也可以使前述研磨头130沿另一方向142横向往复旋转。因此,结合横向运动以及旋转的方式,可以降低前述晶圆S1进行研磨时晶圆S1表面上的移除速率(removal rate)的差异。前述化学机械研磨装置100进一步包含一研磨平台110。前述研磨平台110沿一方向112旋转。一研磨垫111设置在前述研磨平台110上。相较于前述晶圆S1,前述研磨平台110具有较大的表面积,以便容纳固定在前述固定环120上的晶圆S1在前述研磨垫111表面上的横向运动。一研磨浆供应管151设置在前述研磨平台110上,以供应一研磨浆153到前述研磨平台110。前述研磨浆153是透过前述研磨浆供应管151上的一喷嘴152滴到前述研磨垫111的表面上。前述研磨浆153可从一容器或是储存槽(图未示)利用重力的方式供应给前述研磨垫111,或是利用帮浦的方式从前述研磨浆供应管151供应给前述研磨垫111。或者,前述研磨浆153也可以从前述研磨平台110的下方供应给前述研磨垫111,此时前述研磨浆153由下至上的方式流经前述研磨垫111的下表面。在其他实施方式中,前述研磨浆153也可以透过设置在前述固定环120中的喷嘴供应到前述研磨垫111。当前述研磨浆153中的颗粒聚集在一起形成大的颗粒时,前述晶圆S1的表面在研磨时可能会被大的颗粒所划伤。因此,需要研磨浆153中的不符合标准的大颗粒过滤掉。一般来说,一过滤器154会连接至前述研磨浆供应管151以过滤聚集的颗粒或是过大的颗粒。由于研磨浆153中的离子或是研磨过程中累积的静电,前述研磨浆153与前述晶圆S1的表面可能会带有电荷。
在一实施例中,前述研磨垫111为一具有表面电荷的聚胺酯(polyurethane)研磨垫。本实施例的研磨垫111为一包含导电添加物的聚胺酯研磨垫。前述导电添加物使前述研磨垫111的表面具有电荷以优化研磨的效果(例如移除速率、选择性以及凹陷)。请参阅图2A与图2B,为前述研磨垫111的表面电荷在研磨过程中对于研磨效果的影响的示意图。如图2A所示,当研磨一带有正电荷的晶圆S1时,使用带有负电荷的研磨垫111会提升研磨过程的移除速率,因为带有正电荷的晶圆S1与带有负电荷的研磨垫111之间具有吸引力。相反地,如图2B所示,如果研磨垫111带有正电荷时,研磨过程的移除速率会被降低,因为带有正电荷的晶圆S1与带有正电荷的研磨垫111之间具有排斥力。因此,利用调整研磨垫111所带的电荷以及电荷的分布,可以调整研磨的效果(例如移除速率、选择性以及凹陷)。
依据本发明的另一实施例,前述研磨垫111由一组合物所制造。前述组合物包含多个氨基甲酸乙酯预聚物(urethane prepolymers)以及一固化剂(curative或hardener)。前述固化剂用于使前述氨基甲酸乙酯预聚物产生交联反应。前述氨基甲酸乙酯预聚物为多元醇(polyols)与异氰酸酯(isocyanates)进行反应所产生。前述多元醇例如聚醚多元醇(polyether polyols)或聚酯多元醇(polyester polyols);前述异氰酸酯例如双官能基异氰酸酯(bifunctional isocyanates)或多官能基异氰酸酯(polyfunctionalisocyanates)。前述用于产生氨基甲酸乙酯预聚物的异氰酸酯包含二异氰酸甲苯酯(methylene diphenyl diisocyanate,简称MDI)、二苯基甲烷二异氰酸酯(toluenediisocyanate,简称TDI)或其混合物。前述组合物中的硬化剂为一化合物或是化合物之混合物用于使前述氨基甲酸乙酯预聚物产生交联反应后而硬化。具体而言,前述硬化剂与异氰酸酯进行反应,使异氰酸酯链结在一起后产生聚胺酯。前述硬化剂包含4,4'-亚甲基双(2-氯苯胺)(4,4'-methylene-bis(2-chloroaniline),简称MBCA,商品名称为MOCA○R)。在一实施方式中,前述组合物包含15~25重量百分比之MBCA、20~40重量百分比之异氰酸酯、30~50重量百分比之多元醇、以及3~10重量百分比之导电添加物。较佳地,前述氨基甲酸乙酯预聚物(即异氰酸酯与多元醇)在组合物中的之重量百分比为70~90。较佳地,前述导电添加物之重量百分比为5~10。前述组合物中的导电添加物包含碳黑、碳纤维、氧化铝颗粒或其混合物。前述导电添加物带有电荷。前述导电添加物也可以是导电奈米粒子,例如奈米碳粒子(carbon nanoparticles)或是奈米碳管(carbon nanotube)。前述氧化铝颗粒可以是球状氧化铝颗粒。
利用调整导电添加物的重量百分比以及导电添加物所带的电荷,可以调整前述组合物所制成的研磨垫的特性。在一实施例中,前述导电添加物带有正电。因此,包含带有正电的导电添加物的组合物所制成的研磨垫具有正的表面电荷,且对带负电的晶圆具有较高的移除速率。相反地,带有正的表面电荷的研磨垫对带正电的晶圆具有较低的移除速率。在其他实施例中,前述导电添加物带有负电。因此,包含带有负电的导电添加物的组合物所制成的研磨垫带有负的表面电荷,且对带负电的晶圆具有较低的移除速率。相反地,带有负的表面电荷的研磨垫对带正电的晶圆具有较高的移除速率。因此,由本发明各种实施例的组合物所制成的研磨垫带有表面电荷,可与研磨浆及晶圆的电荷产生静电吸引力或排斥力,以此方式可以优化研磨的效果。此外,由本发明各种实施例之组合物所制成的研磨垫的导电度也可以依据不同研磨制程的需要进行调整。
较佳地,前述导电添加物之导电度介于1~30mS/cm之间,且前述导电添加物之界面电位(zeta potential)介于-200~100mV之间。前述异氰酸酯包含二异氰酸甲苯酯(MDI)、二苯基甲烷二异氰酸酯(TDI)或其混合物。前述多元醇为聚四亚甲基醚二醇(poly(tetramethylene ether)glycol,PTMG)。此外,前述组合物中的预聚物一般可用未反应NCO基团的重量百分比来描述其特性。在一实施例中,前述组合物之未反应NCO基团的重量百分比介于0.1~10之间,较佳的重量百分比介于3~10之间。
前述固化剂在组合物中的重量百分比会影响所制造的研磨垫的硬度。一般来说,前述研磨垫的硬度约为60肖氏硬度D(Shore D)。前述用于制造研磨垫的组合物可进一步包含其他的成分,例如表面活性剂、填充剂、催化剂、加工助剂、抗氧化剂、稳定剂或润滑剂。
在其他实施例中,前述研磨垫可为一复合式的研磨垫。请参考图3A与图3B,为各种实施例的复合式研磨垫的上视图。在一实施例中,如图3A所示,前述研磨垫111为一复合式研磨垫,包含一第一研磨垫111a与一第二研磨垫111b。前述第一研磨垫111a带有正的表面电荷,前述第二研磨垫111b带有负的表面电荷。前述第一研磨垫111a与前述第二研磨垫111b由本发明之组合物所制成。具体来说,用于制备前述第一研磨垫111a的组合物的导电添加物带有正电;用于制备前述第二研磨垫111b的组合物的导电添加物带有负电。在另一实施例中,如图3B所示,前述研磨垫111为一复合式研磨垫,包含一第一研磨垫111a、一第二研磨垫111b、一第三研磨垫111c、以及一第四研磨垫111d。前述第一研磨垫111a与前述第四研磨垫111d带有正的表面电荷;前述第二研磨垫111b与前述第三研磨垫111c带有负的表面电荷。具体来说,用于制备前述第一研磨垫111a与前述第四研磨垫111d的组合物的导电添加物带有正电;用于制备前述第二研磨垫111b与前述第三研磨垫111c的组合物的导电添加物带有负电。并且,用于制备前述第一研磨垫111a的组合物中的带电添加物的重量百分比低于前述第四研磨垫111d;且用于制备前述第二研磨垫111b的组合物中的带电添加物的重量百分比高于前述第三研磨垫111c。
请参考图4,为本发明再一实施例之一种制备研磨垫的方法S400的流程图。如图4所示,前述方法S400包含步骤S401至S403。在步骤S401中,提供一用于制备前述研磨垫的组合物。前述组合物可参考前述本发明实施例之组合物。前述组合物包含15~25重量百分比之4,4'-亚甲基双(2-氯苯胺)、20~40重量百分比之异氰酸酯、30~50重量百分比之多元醇以及3~10重量百分比之导电添加物。前述导电添加物包含碳黑、碳纤维、氧化铝颗粒或其混合物。前述导电添加物带有电荷。在步骤S402中,将前述组合物放入一敞口铸型中。举例来说,前述敞口铸型可为一盘状的敞口铸型。在步骤S403中,加热硬化前述组合物以产生一聚胺酯发泡树脂。在一实施例中,前述组合物被加热到90℃到150℃并维持5到10个小时以进行硬化。前述聚胺酯发泡树脂再用裁切的方式切割成不同厚度与形状的研磨垫。
在又一实施例中,本发明提供一种化学机械研磨装置,用于研磨一晶圆。本实施例之化学机械研磨装置可参考图1中的化学机械研磨装置100。前述化学机械研磨装置100包含一研磨平台110、一固定环120、一研磨头130以及一研磨浆供应管151。前述研磨平台110包含一研磨垫111,用于利用一研磨浆153研磨前述晶圆S1。前述固定环120用于固定前述晶圆S1。前述研磨头130连接于前述固定环120,并且用于转动前述固定环120。前述研磨浆供应管151用于供应前述研磨浆153至前述研磨平台110的研磨垫111上。前述化学机械研磨装置100进一步包含一驱动马达140以及一过滤器154。前述驱动马达140连接于前述研磨头130。前述过滤器154连接于前述研磨浆供应管151。前述驱动马达140沿一方向141转动前述研磨头130。前述驱动马达140也可以使前述研磨头130沿另一方向142横向往复旋转。前述过滤器154用于过滤研磨浆153中较大的颗粒(例如聚集的颗粒),以避免较大的颗粒使前述晶圆S1表面产生缺陷。
前述研磨平台110的研磨垫111为一聚胺酯研磨垫,由一组合物所制成。前述组合物可参考前述实施例之组合物。前述组合物包含15~25重量百分比之4,4'-亚甲基双(2-氯苯胺)、20~40重量百分比之异氰酸酯、30~50重量百分比之多元醇以及3~10重量百分比之导电添加物。前述导电添加物包含碳黑、碳纤维、氧化铝颗粒或其混合物。前述导电添加物带有电荷。有关于前述组合物之详细描述以及研磨垫111之制备方法可参考上述实施例。
综上所述,本发明实施例之研磨垫由一包含氨基甲酸乙酯预聚物以及导电添加物之组合物所制备而成。前述组合物中的导电添加物带有电荷。因此,由本发明之组合物所制成的研磨垫具有表面电荷,可与晶圆表面以及研磨浆中的电荷产生静电吸引力或排斥力,以此方式可以优化研磨的效果。
以上所述,仅是本发明的较佳实施方式而已,并非对本发明任何形式上的限制,虽然本发明已是较佳实施方式揭露如上,并非用以限定本发明,任何熟悉本专业的技术人员,在不脱离本发明技术方案范围内,当可利用上述揭示的技术内容做出些许更动或修饰为等同变化的等效实施方式,但凡是未脱离本发明技术方案内容,依据本发明的技术实质对以上实施方式所做的任何简单修改、等同变化与修饰,均仍属于本发明技术方案的范围内。
Claims (10)
1.一种制备研磨垫之组合物,其特征在于,其包含:
15~25重量百分比之4,4'-亚甲基双(2-氯苯胺);
20~40重量百分比之异氰酸酯;
30~50重量百分比之多元醇;以及
3~10重量百分比之导电添加物;
其中,前述导电添加物包含碳黑、碳纤维、氧化铝颗粒或其混合物,前述导电添加物带有电荷。
2.如权利要求1所述的组合物,其特征在于,前述导电添加物之导电度介于1~30mS/cm之间。
3.如权利要求1所述的组合物,其特征在于,前述导电添加物之界面电位介于-200~100mV之间。
4.如权利要求1所述的组合物,其特征在于,前述异氰酸酯包含二异氰酸甲苯酯、二苯基甲烷二异氰酸酯或其混合物。
5.如权利要求1所述的组合物,其特征在于,前述多元醇为聚四亚甲基醚二醇。
6.如权利要求1所述的组合物,其特征在于,前述导电添加物带有正电。
7.如权利要求1所述的组合物,其特征在于,前述导电添加物带有负电。
8.如权利要求1所述的组合物,其特征在于,前述组合物之未反应NCO基团重量百分比介于0.1~10之间。
9.如权利要求8所述的组合物,其特征在于,前述组合物之未反应NCO基团之重量百分比介于3~10之间。
10.如权利要求1所述的组合物,其特征在于,前述导电添加物之重量百分比介于5~10。
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