CN106928860A - 一种用于sti领域的化学机械抛光液及其应用 - Google Patents
一种用于sti领域的化学机械抛光液及其应用 Download PDFInfo
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Abstract
本发明公开了一种应用于STI的CMP抛光液，其包括纳米磨料、高分子聚合物及有机硅化学添加剂。本发明公开的抛光液可达到高的HDP oxide(高密度等离子体二氧化硅)去除速率，以及高的HDP/SiN抛光选择比，具有良好的STI抛光应用前景。
Description
技术领域
本发明涉及一种化学机械抛光液，尤其涉及一种用于STI领域的化学机械抛光液。
背景技术
浅槽隔离(STI)技术是目前IC制造中器件隔离的主要方法。STI工艺步骤主要包括：首先，在基材的预定位置上生成若干槽，通常采用各向异性蚀刻法；其次，在各个槽中沉积二氧化硅；最后，用CMP法抛光二氧化硅，直到向下抛光到并停止在氮化硅层，即形成STI结构。由于STI技术产生的器件隔离效率很容易收到影响，所以对STI的抛光提出了极高的要求，不仅要求很高的HDP oxide(高密度等离子体二氧化硅)的去除速率、很高的氮化硅的抛光速率选择比，同时要求非常低的表面缺陷指标以及不同密度区域的抛光均一性。
目前，二氧化硅和二氧化铈是应用最为广泛的两种CMP研磨剂，但现有报道抛光液中，二氧化硅作为研磨剂的其抛光速率普遍较低，且通常具有较低的二氧化硅/氮化硅抛光选择比(如专利200510116191.9)；而氧化铈磨料虽然具有较高的HDP oxide抛光速率和SiN选择性，但在抛光过程中容易引起划伤(scratch)等缺陷，如专利101065458A中采用氧化铈作为磨料，在阳离子聚合物的协同作用下可实现二氧化硅/氮化硅的高抛光选择比，但该专利并未考虑抛光过程中TEOS表面的划伤问题。
发明内容
为了克服以上问题，本发明公开了一种用于STI抛光的CMP抛光液，其以纳米二氧化硅或二氧化铈为磨料，通过添加有机高分子聚合物和硅烷偶联剂，在实现高的STI抛光选择比的同时，降低或避免了抛光过程中凹陷、划痕等缺陷的出现，具体为：
本发明公开了一种应用于STI抛光的CMP抛光液，其特征在于，包括纳米磨料、高分子聚合物及有机硅化学添加剂。
其中，所述高分子聚合物选自聚羧酸类化合物、有机膦酸类化合物或聚乙烯吡咯烷酮(PVP)类化合物中一种或多种。
其中，所述聚羧酸类化合物选自聚环氧琥珀酸纳(PESA)，聚丙烯酸(PAA)，马来酸-丙烯酸共聚物(MA-AA)，聚丙烯酸钠(PAAS)，水解聚马来酸酐(HPMA)中的一种或多种；所述有机膦酸类化合物选自氨基三甲叉膦酸(ATMP)、羟基乙叉二膦酸(HEDP)、乙二胺四甲叉膦酸(EDTMPA)、二乙烯三胺五甲叉膦酸(DTPMPA)、乙二胺四甲叉膦酸钠(EDTMPS)2-羟基膦酰基乙酸(HPAA)中的一种或多种；所述聚乙烯吡咯烷酮(PVP)类化合物为相对分子量为103-107范围内的一种或多种聚合物；所述聚乙烯吡咯烷酮(PVP)类化合物的K值为15、17、25、30和/或90。
其中，所述高分子聚合物在抛光液中的含量为0.01-1.0wt％；
其中，所述的纳米磨料可以为氧化铈研磨颗粒、硅溶胶颗粒中一种或多种，
其中，所述研磨粒子的含量为0.25-5.0wt％。
其中，其中，所述有机硅类化合物为硅烷偶联剂。
其中，所述硅烷偶联剂结构中可以含有2-3个水解基团，所含水解基团优选为烷氧基，所述硅烷偶联剂分子结构中所含的烷氧基优选为乙氧基，或甲氧基，所述硅烷偶联剂分子结构中可以含有多个非水解有机基团，所述非水解有机基团可以是甲基、氯烃基、氨烃基、乙烯基及环氧烃基中一种或多种。
其中，所述硅烷偶联剂在抛光液中的含量为0.001-0.1wt％。
其中，所述抛光液进一步包括pH值调节剂，所述抛光液的pH值范围为3.0-10.0。
本发明另一方面，公开了上述抛光液在包括氧化硅、氮化硅在内的多种介质表面抛光中的应用。
本发明的积极进步效果在于：本发明的抛光液选用研磨颗粒，结合所选高分子分子聚合物及化学添加剂的协同作用，具有相对较好的STI抛光速率和抛光表面特征。
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。
按照表1中各实施例以及对比实施例的成分及其比例配制抛光液，混合均匀。另外需要说明的是，以下抛光液中使用的磨料为其原始含量为5wt％至50wt％的水分散液。
表1中抛光液的具体调配方式为：将除研磨颗粒外的组分按照表中所列的含量，在去离子水中混合均匀，用KOH调节到所需pH值，然后加入研磨颗粒分散液，若pH下降则用KOH调节到所需的pH值，并用去离子水补足百分含量至100wt％，即可制得化学机械抛光液。
表1本发明实施例及对比例的配方
效果实施例1
为了进一步考察该类抛光液的抛光情况，本发明采用了如下技术手段：分别用上述实施例中抛光液1-10和对比例1-4对空白的HDP oxide(高密度等离子体二氧化硅)和SiN晶片进行抛光，抛光条件相同，抛光参数如下：Logitech抛光垫，向下压力3psi，转盘转速/抛光头转速＝60/80rpm，抛光时间60s，化学机械抛浆料流速100mL/min。抛光所用HDP和SiN晶圆切片均由市售(例如美国SVTC公司生产的)8英寸镀膜晶圆切片而成。抛光所用的HDP和SiN晶圆切片上的HDP和SiN层厚由NAPSON公司生产的RT-7O/RG-7B测试仪测得，用抛光前后测得的厚度差值除以抛光耗用时间即得HDP和SiN去除速率。抛光时间为1分钟。
实施例中未注明具体条件的实验方法，通常按照常规条件，或按照制造厂商所建议的条件进行。
至于刮痕的评价方法为，抛光后，洗涤并干燥HDP和SiN晶圆，随后在暗室的点光源下用肉眼观察存在或不存在刮痕斑点，评价标准如下：
●用肉眼观察不到刮痕斑点
○用肉眼观察不到明显的刮痕斑点
×用肉眼观察到一些刮痕斑点，但它们还不至于达到造成质量问题的量
△用肉眼观察到明显的刮痕斑点，并且达到造成质量问题的量
具体结果如表2所示：
表2实施例1-10和对比例1-4的抛光效果
从表2可以看出，实施例1-5中，通过氧化铈磨料以及特定氧化剂，络合剂以及腐蚀抑制剂的复配，和对比实施例1-4相比，具有相对较好的铜抛光速率和抛光表面特征。
应当理解的是，本发明所述wt％均指的是质量百分含量。
以上对本发明的具体实施例进行了详细描述，但其只是作为范例，本发明并不限制于以上描述的具体实施例。对于本领域技术人员而言，任何对本发明进行的等同修改和替代也都在本发明的范畴之中。因此，在不脱离本发明的精神和范围下所作的均等变换和修改，都应涵盖在本发明的范围内。
Claims (17)
1.一种用于STI领域的化学机械抛光液，其特征在于，包括纳米磨料、高分子聚合物及有机硅化学添加剂。
2.如权利要求1所述的用于STI领域的化学机械抛光液，其特征在于，所述高分子聚合物选自聚羧酸类化合物、有机膦酸类化合物或聚乙烯吡咯烷酮(PVP)类化合物中一种或多种。
3.如权利要求2所述的用于STI领域的化学机械抛光液，其特征在于，所述聚羧酸类化合物选自聚环氧琥珀酸纳(PESA)，聚丙烯酸(PAA)，马来酸-丙烯酸共聚物(MA-AA)，聚丙烯酸钠(PAAS)，水解聚马来酸酐(HPMA)中的一种或多种。
4.如权利要求2所述的用于STI领域的化学机械抛光液，其特征在于，所述有机膦酸类化合物选自氨基三甲叉膦酸(ATMP)、羟基乙叉二膦酸(HEDP)、乙二胺四甲叉膦酸(EDTMPA)、二乙烯三胺五甲叉膦酸(DTPMPA)、乙二胺四甲叉膦酸钠(EDTMPS)2-羟基膦酰基乙酸(HPAA)中的一种或多种。
5.如权利要求2所述的用于STI领域的化学机械抛光液，其特征在于，所述聚乙烯吡咯烷酮(PVP)类化合物的相对分子量的范围为103-107。
6.如权利要求2所述的用于STI领域的化学机械抛光液，其特征在于，所述聚乙烯吡咯烷酮(PVP)类化合物的K值为15、17、25、30和/或90。
7.如权利要求1所述的用于STI领域的化学机械抛光液，其特征在于，所述高分子聚合物的含量为0.01-1.0wt％。
8.如权利要求1所述的用于STI领域的化学机械抛光液，其特征在于，所述纳米磨料为氧化铈研磨颗粒、硅溶胶颗粒中一种或多种。
9.如权利要求1所述的用于STI领域的化学机械抛光液，其特征在于，所述研磨颗粒的含量为0.25-5.0wt％。
10.如权利要求1所述的用于STI领域的化学机械抛光液，其特征在于，所述有机硅类添加剂为硅烷偶联剂。
11.如权利要求10所述的用于STI领域的化学机械抛光液，其特征在于，所述硅烷偶联剂分子结构中含有2-3个水解基团，所述水解基团为烷氧基。
12.如权利要求10所述的用于STI领域的化学机械抛光液，其特征在于，所述硅烷偶联剂分子结构中所含烷氧基为乙氧基，或甲氧基。
13.如权利要求10所述的用于STI领域的化学机械抛光液，其特征在于，所述硅烷偶联剂分子结构中含有多个非水解有机基团，所述非水解有机基团为甲基、氯烃基、氨烃基、乙烯基及环氧烃基中一种或多种。
14.如权利要求1所述的用于STI领域的化学机械抛光液，其特征在于，所述硅烷偶联剂的含量为0.001-0.1wt％。
15.如权利要求1所述的用于STI领域的化学机械抛光液，其特征在于，所述抛光液进一步包括pH值调节剂。
16.如权利要求1所述的用于STI领域的化学机械抛光液，其特征在于，所述抛光液的pH值为3.0-10.0。
17.一种如权利要求1-17任一项所述的用于STI领域的化学机械抛光液，在包括氧化硅、氮化硅的介质表面抛光中的应用。
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