CN1660923A - 化学机械抛光氧化硅和氮化硅的组合物与方法 - Google Patents
化学机械抛光氧化硅和氮化硅的组合物与方法 Download PDFInfo
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- CN1660923A CN1660923A CN200510052407XA CN200510052407A CN1660923A CN 1660923 A CN1660923 A CN 1660923A CN 200510052407X A CN200510052407X A CN 200510052407XA CN 200510052407 A CN200510052407 A CN 200510052407A CN 1660923 A CN1660923 A CN 1660923A
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- silicon nitride
- silicon oxide
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Abstract
本发明提供可用于抛光在半导体晶片上的氧化硅和氮化硅的含水组合物，它包括以重量百分数计，0.01－5的两性离子化合物，0.01－5的羧酸聚合物，0.02－6的磨蚀剂，0－5的阳离子化合物和余量的水，其中该两性离子化合物具有下述结构：其中n为整数，Y包括氢或烷基，Z包括羧基、硫酸盐或氧，M包括氮、磷或硫原子，和X1、X2和X3独立地包括选自氢、烷基和芳基中的取代基。
Description
发明背景
[0001]本发明涉及半导体晶片材料的化学机械平面化(CMP)，和更特别地涉及在浅槽分离(STI)工艺中抛光来自半导体晶片的氧化硅和氮化硅的CMP组合物和方法。
[0002]减少器件尺寸和增加微电子电路内的集成化密度已要求相应降低孤立结构的尺寸。这种降低助长了提供有效隔离的结构的可重复形成，同时占据最小量的基底表面。
[0003]STI技术是一种广泛使用的半导体制造方法，以供形成孤立结构，电隔离在集成电路内形成的各种有源组件。使用STI技术相对于常规LOCOS(硅的局部氧化)技术的一个主要优点是，CMOS(互补金属氧化物半导体)IC器件的高可量测性，以供在亚微米的集成化水平下制造。另一优点是，STI技术辅助防止出现所谓的鸟嘴侵入(encroachment)，所述鸟嘴侵入是形成孤立结构的LOCOS技术的特征。
[0004]在STI技术中，第一步是在基底的预定位置处，通常通过各向异性蚀刻，形成多个沟槽。接下来，氧化硅沉积在这些沟槽中的每一个内。然后通过CMP抛光氧化硅，向下一直到氮化硅(终止层)上，形成STI结构。为了实现有效的抛光，抛光浆料必须提供高选择性，所述高选择性包括相对于氮化硅，氧化硅的除去速度(“选择性”)。
[0005]Kido等在美国专利申请公开No.2002/0045350中公开了一种含氧化铈和水溶性有机化合物的已知磨蚀组合物，用以抛光半导体器件。任选地，该组合物含有粘度调节剂、缓冲液、表面活性剂和螯合剂，但没有具体公开任何一种。尽管Kido的组合物提供充分的选择性，但在微电子电路中愈来愈增加的集成化密度要求改进的组合物和方法。
[0006]因此，所需要的是化学机械抛光氧化硅和氮化硅的组合物和方法，用于具有改进选择性的浅槽分离工艺。
本发明的描述
[0007]在第一方面中，本发明提供可用于抛光在半导体晶片上的氧化硅和氮化硅的含水组合物，它包括以重量百分数计，0.01-5的两性离子化合物，0.01-5的羧酸聚合物，0.02-6的磨蚀剂，0-5的阳离子化合物和余量的水，其中该两性离子化合物具有下述结构：
其中n为整数，Y包括氢或烷基，Z包括羧基、硫酸根或氧，M包括氮、磷或硫原子，和X1、X2和X3独立地包括选自氢、烷基和芳基中的取代基。
[0008]在第二方面中，本发明提供可用于抛光在半导体晶片上的氧化硅和氮化硅的含水组合物，它包括以重量百分数计，0.01-5的N，N，N-三甲基乙酸铵(ammonioacetate)，0.01-5的聚丙烯酸聚合物，0.02-6的二氧化铈，0-5的阳离子化合物和余量的水，其中该含水组合物的pH为4-9。
[0009]在第三方面中，本发明提供抛光在半导体晶片上的氧化硅和氮化硅的方法，该方法包括：使在晶片上的氧化硅和氮化硅与抛光组合物接触，该抛光组合物包括以重量百分数计，0.01-5的两性离子化合物，0.01-5的羧酸聚合物，0.02-6的磨蚀剂，0-5的阳离子化合物和余量的水；用抛光垫(pad)抛光氧化硅和氮化硅；和其中该两性离子化合物具有下述结构：
其中n为整数，Y包括氢或烷基，Z包括羧基、硫酸根或氧，M包括氮、磷或硫原子，和X1、X2和X3独立地包括选自氢、烷基和芳基中的取代基。
发明详述
[0010]该组合物和方法提供相对于氮化硅除去氧化硅的预料不到的选择性。该组合物有利地依赖于螯合剂或选择性提高剂，相对于氮化硅选择抛光氧化硅用于浅槽分离工艺。特别地，该组合物包括两性离子化合物，以便在应用的pH下相对于氮化硅选择抛光氧化硅。
[0011]如此处所定义的，术语“烷基”是指优选含有1-20个碳原子的取代或未取代的、直链、支链或环状烃链。烷基包括例如甲基、乙基、丙基、异丙基、环丙基、丁基、异丁基、叔丁基、仲丁基、环丁基、戊基、环戊基、己基和环己基。
[0012]术语“芳基”是指优选含有6-20个碳原子的取代或未取代的芳族碳环基。芳基可以是单环或多环芳基。芳基包括例如苯基、萘基、联苯基、苄基、甲苯基、二甲苯基、苯乙基、苯甲酸根、烷基苯甲酸根、苯胺和N-烷基苯胺基。
[0013]术语“两性离子化合物”是指含有通过物理桥，例如CH2基连接的相等比例的阳离子和阴离子取代基的化合物，以便该化合物总体为净中性。本发明的两性离子化合物包括下述结构：
其中n为整数，Y包括氢或烷基，Z包括羧基、硫酸根或氧，M包括氮、磷或硫原子，和X1、X2和X3独立地包括选自氢、烷基和芳基中的取代基。
[0014]优选的两性离子化合物包括例如甜菜碱。本发明的优选甜菜碱是用下述结构表示的N，N，N-三甲基乙酸铵：
[0015]该组合物有利地含有0.01-5wt％的两性离子化合物，以便相对于氮化硅，选择除去氧化硅。有利地，该组合物含有0.05-1.5wt％的两性离子化合物。本发明的两性离子化合物可有利地促进平面化(planarization)和可抑制氮化物的除去。
[0016]除了两性离子化合物以外，该组合物还有利地含有0.01-5wt％的羧酸聚合物。优选地，该组合物含有0.05-1.5wt％的羧酸聚合物。此外，聚合物的数均分子量优选为4000-1500000。另外，可使用较高和较低数均分子量的羧酸聚合物的共混物。这些羧酸聚合物通常为溶液形式，但可以是水分散液形式。羧酸聚合物有利地充当(以下所述的)磨蚀剂颗粒的分散剂。通过GPC(凝胶渗透色谱法)测定前述聚合物的数均分子量。
[0017]由不饱和单羧酸和不饱和二羧酸形成羧酸聚合物。典型的不饱和单羧酸单体含有3-6个碳原子和包括丙烯酸、低聚丙烯酸、甲基丙烯酸、巴豆酸和乙烯基乙酸。典型的不饱和二羧酸含有4-8个碳原子和包括其酸酐，和例如是马来酸、马来酸酐、富马酸、戊二酸、衣康酸、衣康酸酐和环己烯二羧酸。另外，也可使用前述酸的水溶性盐。
[0018]特别有用的是数均分子量为约1000-1500000，优选3000-250000，和更优选20000-200000的“聚(甲基)丙烯酸”。此处所使用的术语“聚(甲基)丙烯酸”定义为丙烯酸的聚合物、甲基丙烯酸的聚合物或丙烯酸和甲基丙烯酸的共聚物。特别优选各种数均分子量的聚(甲基)丙烯酸的共混物。在聚(甲基)丙烯酸的这些共混物或混合物中，与数均分子量为150000-1500000，优选200000-300000的较高数均分子量的聚(甲基)丙烯酸结合使用数均分子量为1000-100000和优选4000-40000的较低数均分子量的聚(甲基)丙烯酸。典型地，较低数均分子量的聚(甲基)丙烯酸对较高数均分子量的聚(甲基)丙烯酸的重量百分比为约10∶1到1∶10，优选5∶1到1∶5，和更优选3∶1到2∶3。优选的共混物包括重量比为2∶1的数均分子量为约20000的聚(甲基)丙烯酸和数均分子量为约200000的聚(甲基)丙烯酸。
[0019]另外，可使用其中羧酸组分占聚合物重量5-75％的含有羧酸的共聚物和三元共聚物。这种聚合物典型的是(甲基)丙烯酸和丙烯酰胺或甲基丙烯酰胺的聚合物；(甲基)丙烯酸和苯乙烯和其它乙烯基芳族单体的聚合物；(甲基)丙烯酸烷酯(丙烯酸或甲基丙烯酸的酯)和单或二羧酸，如丙烯酸或甲基丙烯酸或衣康酸的聚合物；具有取代基如卤素(即氯、氟、溴)、硝基、氰基、烷氧基、卤代烷基、羧基、氨基、氨基烷基的取代乙烯基芳族单体和不饱和的单或二羧酸和(甲基)丙烯酸烷酯的聚合物；含有氮环的单烯键式不饱和单体，如乙烯基吡啶、烷基乙烯基吡啶、乙烯基丁内酯、乙烯基己内酰胺，和不饱和单或二羧酸的聚合物；烯烃，如丙烯、异丁烯或具有10-20个碳原子的长链烷基烯烃和不饱和单或二羧酸的聚合物；乙烯醇酯，如乙酸乙烯酯和硬脂酸乙烯酯或卤乙烯，如氟乙烯、氯乙烯、偏氟乙烯或乙烯腈类，如丙烯腈和甲基丙烯腈和不饱和单或二羧酸的聚合物；在烷基中具有1-24个碳原子的(甲基)丙烯酸烷酯和不饱和单或二羧酸，如丙烯酸或甲基丙烯酸的聚合物。这些仅仅是可在本发明的新型抛光组合物中使用的各种聚合物的一些实例。此外，可使用可生物降解、可光降解或通过其它方式可降解的聚合物。可生物降解的这种组分的实例是含有聚(丙烯酸酯共2-氰基丙烯酸甲酯)链段的聚丙烯酸聚合物。
[0020]有利地，抛光组合物含有0.2-6wt％的磨蚀剂以促进氧化硅的除去。在这一范围内，理想的是具有以大于或等于0.5wt％的用量存在的磨蚀剂。此外，在这一范围内理想的是小于或等于2.5wt％的用量。
[0021]磨蚀剂的平均粒度为50-200纳米(nm)。为了此处说明的目的，粒度是指磨蚀剂的平均粒度。更优选，理想的是使用平均粒度为80至150nm的磨蚀剂。降低磨蚀剂的尺寸到小于或等于80nm倾向于改进抛光组合物的平面化，但它也倾向于降低除去速度。
[0022]磨蚀剂的实例包括无机氧化物、无机氢氧化物、金属硼化物、金属碳化物、金属氮化物、聚合物颗粒和含至少一种前述物质的混合物。合适的无机氧化物包括例如氧化硅(SiO2)、氧化铝(Al2O3)、氧化锆(ZrO2)、二氧化铈(CeO2)、氧化锰(MnO2)或含至少一种前述氧化物的混合物。也可视需要使用这些无机氧化物的改性形式，如聚合物涂布的无机氧化物颗粒和无机涂布颗粒。合适的金属碳化物、硼化物和氮化物包括，例如碳化硅、氮化硅、碳氮化硅(SiCN)、碳化硼、碳化钨、碳化锆、硼化铝、碳化钽、碳化钛或含有至少一种前述金属碳化物、硼化物和氮化物的混合物。视需要，金刚石也可用作磨蚀剂。可供替代的磨蚀剂还包括聚合物颗粒和涂布的聚合物颗粒。优选的磨蚀剂是二氧化铈。
[0023]该化合物在宽的pH范围内在含有余量水的溶液中提供功效。该溶液的有用pH范围从至少4延伸到9。另外，该溶液有利地依赖于余量的去离子水限制附随的杂质。本发明的抛光流体的pH优选为4.5-8，更优选pH为5.5-7.5。调节本发明组合物pH所使用的酸例如是硝酸、硫酸、盐酸、磷酸和类似物。调节本发明pH所使用的例举碱例如是氢氧化铵和氢氧化钾。
[0024]任选地，本发明的组合物可包括0-5wt％的阳离子化合物。优选地，该组合物任选地包括0.05-1.5wt％的阳离子化合物。本发明的阳离子化合物可有利地促进平面化，调节晶片的清洁时间和起到抑制氧化物除去的作用。优选的阳离子化合物包括烷胺、芳基胺、季铵化合物和醇胺。例举的阳离子化合物包括甲胺、乙胺、二甲胺、二乙胺、三甲胺、三乙胺、苯胺、四甲基氢氧化铵、四乙基氢氧化铵、乙醇胺和丙醇胺。
[0025]因此，本发明提供可用于抛光在半导体晶片上的氧化硅和氮化硅的组合物以供浅槽分离工艺。该组合物有利地包括改进选择性用的两性离子化合物。特别地，本发明提供可用于抛光在半导体晶片上的氧化硅和氮化硅的含水组合物，它包括0.01-5的两性离子化合物，0.01-5的羧酸聚合物，0.02-6的磨蚀剂，0-5的阳离子化合物和余量的水。该组合物4-9的pH范围内显示出尤其改进的选择性。
实施例
[0026]在实施例中，数字表示本发明的实施例和字母表示对比例。所有实施例的溶液含有以重量百分数为单位计，1.8的二氧化铈和0.18的多羧酸。
实施例1
[0027]该实验测量在半导体晶片上相对于氮化硅，氧化硅的选择性。特别是，测试甜菜碱(N，N，N-三甲基乙酸铵)对相对于氮化硅，氧化硅的选择性的影响。在约5psi的向下力条件和150cc/min的抛光溶液流速，52RPM的台板速度和50RPM的载体速度，使用IC 1000TM聚氨酯抛光垫(Rohm and Haas Electronic Materials CMP Technologies)的IPEC472 DE 200mm抛光机，平面化样品。抛光溶液具有用硝酸或氢氧化铵调节的6.5的pH。所有溶液含有去离子水。
表1
| 试验 | 磨蚀剂(wt％) | PAA(wt％) | 甜菜碱(wt％) | 乙醇胺(wt％) | TEOS(埃/分钟) | SiN(埃/分钟) | 选择率 |
| A | 1.8 | 0.18 | - | - | 3200 | 80 | 40 |
| 1 | 1.8 | 0.18 | 0.5 | - | 3000 | 45 | 66 |
| B | 1.8 | 0.18 | - | 0.3 | 1850 | 130 | 14 |
| 3 | 1.8 | 0.18 | 0.5 | 0.3 | 2500 | 130 | 19 |
[0028]如上表1所示，添加两性离子化合物改进组合物的选择率。特别是添加N，N，N-三甲基乙酸铵改进试验1中组合物对TEOS相对于氮化硅的选择率，从40(试验A)到66。添加N，N，N-三甲基乙酸铵抑制氮化硅，在试验A和试验1中分别为80埃/分钟和45埃/分钟。添加乙醇胺抑制TEOS的除去速度，在试验A和试验B中分别为3200埃/分钟和1850埃/分钟。
[0029]因此，本发明提供可用于抛光在半导体晶片上的氧化硅和氮化硅的组合物以供浅槽分离工艺。该组合物有利地包括在抛光工艺过程中改进的选择性和可控性用的两性离子化合物。特别地，本发明提供可用于抛光在半导体晶片上的氧化硅和氮化硅的含水组合物，它包括两性离子化合物，羧酸聚合物，磨蚀剂，和余量的水。任选地，本发明的组合物可含有阳离子化合物以促进平面化，调节晶片的清洁时间和氧化硅的除去。
Claims (10)
1.一种可用于抛光在半导体晶片上的氧化硅和氮化硅的含水组合物，它包括以重量百分数计，0.01-5的两性离子化合物，0.01-5的羧酸聚合物，0.02-6的磨蚀剂，0-5的阳离子化合物和余量的水，该两性离子化合物具有下述结构：
其中n为整数，Y包括氢或烷基，Z包括羧基、硫酸根或氧，M包括氮、磷或硫原子，和X1、X2和X3独立地包括选自氢、烷基和芳基中的取代基。
2.权利要求1的组合物，其中该两性离子化合物具有下述结构：
3.权利要求1的组合物，其中阳离子化合物选自烷胺、芳基胺、季铵化合物和醇胺。
4.权利要求1的组合物，其中磨蚀剂是二氧化铈。
5.权利要求4的组合物，其中二氧化铈的平均粒度为50-200nm。
6.权利要求1的组合物，其中含水组合物的pH为4-9。
7.可用于抛光在半导体晶片上的氧化硅和氮化硅的含水组合物，它包括以重量百分数计，0.01-5的N，N，N-三甲基乙酸铵，0.01-5的聚丙烯酸聚合物，0.02-6的二氧化铈，0-5的阳离子化合物和余量的水，其中该含水组合物的pH为4-9。
8.一种抛光在半导体晶片上的氧化硅和氮化硅的方法，该方法包括：
使在晶片上的氧化硅和氮化硅与抛光组合物接触，该抛光组合物包括以重量百分数计，0.01-5的两性离子化合物，0.01-5的羧酸聚合物，0.02-6的磨蚀剂，0-5的阳离子化合物和余量的水；
用抛光垫抛光氧化硅和氮化硅；和
其中该两性离子化合物具有下述结构：
其中n为整数，Y包括氢或烷基，Z包括羧基、硫酸根或氧，M包括氮、磷或硫原子，和X1、X2和X3独立地包括选自氢、烷基和芳基中的取代基。
9.权利要求8的方法，其中该两性离子化合物具有下述结构：
10.权利要求8的方法，其中阳离子化合物选自烷胺、芳基胺、季铵化合物和醇胺。
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| US10/788,654 US20050189322A1 (en) | 2004-02-27 | 2004-02-27 | Compositions and methods for chemical mechanical polishing silica and silicon nitride |
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| CN103180101A (zh) * | 2010-08-23 | 2013-06-26 | 福吉米株式会社 | 研磨用组合物及使用其的研磨方法 |
| CN111334193A (zh) * | 2018-12-19 | 2020-06-26 | 富士胶片电子材料美国有限公司 | 抛光组合物及其使用方法 |
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| JP2005252255A (ja) | 2005-09-15 |
| DE102005006614A1 (de) | 2005-10-13 |
| FR2867194A1 (fr) | 2005-09-09 |
| US20070007248A1 (en) | 2007-01-11 |
| CN100339420C (zh) | 2007-09-26 |
| TW200539351A (en) | 2005-12-01 |
| KR20060042396A (ko) | 2006-05-12 |
| FR2867194B1 (fr) | 2006-10-20 |
| US20050189322A1 (en) | 2005-09-01 |
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