CN1211448C - 在二氧化硅化学机械抛光过程中减少/消除划痕和缺陷的组合物和方法 - Google Patents
在二氧化硅化学机械抛光过程中减少/消除划痕和缺陷的组合物和方法 Download PDFInfo
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- H01L21/31053—Planarisation of the insulating layers involving a dielectric removal step
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Abstract
一种用于化学机械抛光二氧化硅工件的水性无浆组合物,其包括:能在中性至碱性pH条件下溶解和离解的阳离子表面活性剂,其中阳离子表面活性剂在水性无浆组合物中的存在量低于其临界胶束浓度。
Description
发明背景
1.发明领域
本发明涉及在二氧化硅薄片表面化学机械抛光过程(CMP)中,阳离子表面活性剂在无浆环境中的应用,以基本上消除或减少在CMP过程中产生的划痕和缺陷.
在VLSI(超大规模集成)加工过程中,在所有的pH条件下,即在酸性、中性和碱性pH条件下,某些类型的阳离子表面活性剂能化学吸附在薄片的二氧化硅部分上。
2.对现有技术的说明
近年来,已经开始使用新的化学机械抛光(CMP)技术对硅晶片表面实施无浆抛光方案,其中抛光板具有嵌入其中的研磨剂颗粒。特别是,对于二氧化硅CMP的应用,抛光板包含用作磨料的CeO2。
在CMP过程中,待抛光的晶片,在有水的环境下对着抛光板面进行研磨。然而,在CMP过程中,在中性或碱性条件下,这些抛光盘能产生缺陷和划痕,因而造成产率下降。
因此,需要设计保护二氧化硅晶片表面以防止在无浆CMP过程中因研磨而产生划痕和缺陷的组合物和方法。
Somasundaran等人在“表面活性剂在固-液界面上的吸附和对链长机制的关系”,物理化学杂志(J.Phys.Chem.),68卷,3562-3566页(1964)中公开:
a)中和二氧化硅上的表面电荷所需的表面活性剂浓度,随链长的增加而下降;和
b)根据中和该表面电荷的临界浓度(是根据在水溶液中对二氧化硅颗粒O Zeta电位的测量间接观测的),每个CH2基团的范德华能量标度为0.97kT或580cal/mol。
根据Somasundaran等人的观点,似乎与吸附在二氧化硅表面上的烷基链之间具有侧向疏水键有关。
美国专利5,769,689公开了在用于抛光由二氧化硅组成的加工件的方法中使用的组合物,其中加工件的表面暴露在包含水、亚微细SiO2颗粒、和可溶性无机盐的抛光组合物中,浓度低于组合物的临界凝聚浓度,其中通过加入可溶性胺,将组合物的pH调节到约9-10。
Kumar等人在“铜在甘油基浆体中的化学-机械抛光”,Mat.Res.Symp.Proc.(材料研究专题讨论会文集),427卷,237-242页(1996)中公开了对金属铜表面的CMP加工,应用包含甘油和Al2O3研磨剂的浆体,使铜适合用作连接件制造。用这种方法代替铜的反应性离子蚀刻方法。
在美国专利5,607,718中公开,对SLI(大规模集成)的化学-机械抛光技术,提出了表面凹陷的问题,其中加入许多化合物以降低溶液的速度和抑制表面凹陷。这些化合物包括若干种增稠剂,例如硅酸盐、葡萄糖、黄蓍胶和琼脂。
Nojo等人在“自停止,无凹陷的SiO2-CMP浆体技术”,IEDM,349-352页,1996 IEEE中公开一种浆体,其中将有表面活性剂的浆体加入到用于SiO2化学机械抛光(CMP)的常规CeO2浆体中,在没有任何终止层或设计限制的情况下,在一个芯片内获得完全的平面化。
美国专利4,588,474公开一种对金属表面清洁处理的方法,其中将甘油与其它添加剂一道加入溶液中,获得更光滑更均匀的表面。这些溶液包含苛性碱、硝酸盐或亚硝酸盐,以及还可有二元醇或多元醇如乙二醇或甘油,加工件是铝合金。
在美国专利5,567,300中公开了在微电子制造的各个阶段中,各种部件的金属去除和平面化的电化学抛光技术。该专利是针对特征清除,并采用非粘性的多元醇来增强清除。在电蚀刻中,采用在室温下粘度是水1500倍的甘油,以提高电解质的粘度和促进抛光。
在前述专利和参考文献中的这些方法中,一个明显的缺点是没有报导需通过对含水介质的化学改进来改善二氧化硅在无浆系统中化学机械抛光(CMP)中的缺陷控制。
发明概述
本发明的一个目的是在采用无浆系统进行化学机械抛光过程中,提供对二氧化硅改善缺陷的控制,以减少或消除与抛光有关的划痕和缺陷。
本发明的另一个目的是在采用无浆系统进行化学机械抛光过程中,通过加入在中性和碱性pH条件下能化学吸附在二氧化硅表面上的特种阳离子表面活性剂提供对二氧化硅改善缺陷的控制。
本发明的另一个目的,是在采用无浆系统进行化学机械抛光过程中,通过在无浆系统中加入阳离子表面活性剂,提供对二氧化硅改善缺陷的控制,这些阳离子表面活性剂,选自下列能产生阳离子的阳离子表面活性剂:
烷基-三甲基-卤化铵;烷基-苄基-二甲基-卤化铵;吡啶-烷基卤;烷基-铵酯;和它们的混合物。可以改变阴离子基团,以获得相应阳离子表面活性剂的离子。
本发明一般是在二氧化硅晶片在中性或碱性条件下化学机械抛光之前,在无浆系统中加入阳离子表面活性剂实现的,这些表面活性剂选自:烷基一三甲基-卤化铵;烷基-苄基-二甲基-卤化铵;吡啶-烷基卤;烷基-铵酯,和它们的混合物,其用量低于临界胶束浓度(超过该浓度,表面活性剂往往倾向于自身聚集)或低于0.1mol/l。
本发明涉及一种用于二氧化硅工件的化学机械抛光的水性无浆组合物,其包括:能在中性至碱性的pH条件下溶解和离解的阳离子表面活性剂,所述的阳离子表面活性剂以水性无浆组合物的形式存在,其含量低于其临界胶束浓度。
本发明还涉及一种减少二氧化硅工件在化学机械抛光过程中的划痕和缺陷的方法,其包括:将所述工件的表面暴露在包含阳离子表面活性剂的无浆抛光组合物中,该阳离子表面活性剂,能在中性至碱性的pH条件下溶解和离解,所述的阳离子表面活性剂在水性无浆组合物中的存在量低于其临界胶束浓度。
在一种优选的实施方案中,所述阳离子表面活性剂是溴化物。
附图简述
图1是表示烃链长度,对石英在烷基乙酸铵溶液和在乙酸铵溶液中Zeta-电位的影响曲线。
发明详述
通过下面对本发明优选实施方案的详细说明,能更好地理解本发明前述的和其它的目的和优点。
为了在采用无浆系统进行的化学机械抛光过程(CMP)中,保护二氧化硅晶片或提供改善的缺陷控制,加入某些种类的阳离子表面活性剂,以减少抛光划痕和缺陷。这些阳离子表面活性剂在中性和碱性pH条件下化学吸附在二氧化硅的表面上,从而保护晶片表面,以防止产生抛光划痕和缺陷。待抛光的晶片对着抛光板的表面研磨,抛光板一般包含嵌入其中的CeO2作为研磨材料。
在化学机械抛光采用的加工系统中,抛光采用的水溶液既可以是中性的,也可以是碱性的,虽然不希望本发明工作受任何理论上的约束,但确信,加入的阳离子表面活性剂,化学吸附在二氧化硅的表面上,能影响二氧化硅表面和带正电荷的端基之间的相互结合。
在本发明情况下有效的四类阳离子表面活性剂,选自:1)烷基-三甲基-卤化铵,其烷基长度为C6-C18,其中优选十六烷基-三甲基-溴化铵;2)烷基-苄基-二甲基-卤化铵,其烷基长度为C6-C18,其中优选十六烷基-苄基-二甲基-溴化铵和十二烷基-苄基-二甲基-溴化铵;3)吡啶鎓-烷基卤,其烷基为C6-C18,其中优选十六烷基氯化吡啶鎓;和4)烷基-铵酯,其烷基为C6-C18,其中优选十二烷基乙酸铵;和它们的混合物。
在本发明的情况下,可以利用阳离子表面活性剂的混合物,以制成复合溶液。采用另一种方案,也可使这四类阳离子表面活性剂中的一种或多种以占优势量存在的表面活性剂混合物与少量的阴离子和/或非离子表面活性剂混合。
在文献中已经确认,阳离子表面活性剂能强烈化学吸附在二氧化硅表面上的现象,并用烷基胺与SiO2的相互作用解释阳离子表面活性剂吸附的实例。吸附自由能具有二个主要项:电相互作用项,该项包括硅表面和带正电荷的端基之间的相互结合;和范德华项,该项包括在前面提到的Somasundaran等人的文献中所指出的,从水溶液中除去疏水基团所需的能量。在Somasundaran等人的文献中,得到以下几点:
A)中和表面电荷所需的表面活性剂浓度(如图1中的曲线所示,该曲线示出,烃链长度对石英在烷基乙酸铵溶液和乙酸铵溶液中Zeta-电位的影响);和
B)中和表面电荷的临界浓度(是根据对二氧化硅颗粒在水溶液中O Zeta-电位的测量间接确定的),根据范德华能量标度估计,每个CH2基团为0.57kT或580cal/mol。
这表明,吸附在二氧化硅表面上的烷基链之间有一个侧向疏水键。Zeta-电位反向所需的临界浓度也随链长的增加而降低。
在上述四类表面活性剂的情况下,CMC或临界胶束浓度(超过该浓度,表面活性剂倾向于自身聚集)低于0.1mol/l。
表I是一些烷基-三甲基卤化铵和烷基-卤化吡啶鎓的临界胶束浓度。
表I
表面活性剂 | 溶剂 | CMC(mol/l) |
十二烷基-三甲基溴化铵 | 25℃的水 | 1.6E-2 |
十二烷基-氯化吡啶鎓 | 25℃的水 | 1.5E-2 |
十四烷基-三甲基氯化铵 | 30℃的水 | 3.5E-3 |
十四烷基-溴化吡啶鎓 | 30℃的水 | 2.6E-3 |
十六烷基-三甲基氯化铵 | 30℃的水 | 1.3E-3 |
十六烷基-氯化吡啶鎓 | 25℃的水 | 9.0E-4 |
从表1可以看出,临界胶束浓度(CMC)随链长的增加而降低。
因此,在本发明的情况下,在采用无浆抛光流程的化学机械抛光装置中,应用这四类阳离子化合物,需要的有效浓度低于0.1mol/l。
尤其是,对不同的链长度,有效浓度是不同的,因此,获得O Zeta-电位值和较高值所需的浓度是最有效的,这些浓度一般在0.01-1mmol/l之间。对于所选择的特定表面活性剂,阳离子表面活性剂的浓度优选低于临界胶束浓度(CMC)。
在本发明另一个实施方案中,可将低浓度的普通阴离子聚合物与在无浆系统中含量占优势的阳离子表面活性剂一起使用。采用阴离子聚合物是有效的,因为化学机械抛光装置的抛光板可以有嵌入其中的CeO2颗粒,当它们在CMP操作过程中从板上脱落时,必须包覆这些颗粒。对于这些情况,可以与含水系统的阳离子表面活性剂一起使用的如聚丙烯酸或丙烯酸铵之类的普通阴离子聚合物的低浓度要低于2重量%,更优选约0.01至约1重量%。
为了进一步减少在采用无浆系统的CMP过程中二氧化硅晶片上的缺陷/划痕,可以将非离子聚合物如分子量<10,000的聚丙烯酰胺或聚乙烯醇加入到表面活性剂混合物的复合溶液中,其浓度低于1重量%,更优选其含量为约0.01重量%。
在这四类阳离子表面活性剂中,一些表面活性剂的毒性数据和LD-50值,按照对小鼠的测定,示于表II。
表II
表面活性剂 | 平均LD-50值(mg/Kg) |
十二烷基-三甲基氯化铵 | 250-300 |
十六烷基-三甲基氯化铵 | 250-300 |
十六烷基-三甲基溴化铵 | 1000 |
癸基-二甲基-苄基氯化铵 | 740 |
十二烷基-二甲基-苄基氯化铵 | 910 |
十六烷基-二甲基-苄基氯化铵 | 1000 |
十八烷基-二甲基-苄基氯化铵 | 3500 |
十六烷基-氯化吡啶鎓 | 200 |
应当指出,在浓度低于1%时,人类使用,对健康没有任何问题。
从以上所述,可以清楚地看到,化学吸附在二氧化硅表面上的胺基阳离子表面活性剂,对吸附自由能的贡献约为1kT,Zeta-电位随表面活性剂的增加向正值变化。
因此,包含表面活性剂,主要是阳离子表面活性剂,和较少的阴离子和/或非离子表面活性剂混合物的水溶液,在中性或碱性条件下在薄片表面的二氧化硅部分上吸附,以形成表面活性剂覆盖的保护层,从而在无浆CMP操作中减少了划痕或抛光缺陷。
虽然上述的实例都集中在二氧化硅晶片上,但应当理解,对其它掺杂的二氧化硅,例如磷硅酸硼玻璃,也可使用本发明的组合物。
本领域的技术人员会很容易发现本发明的另一些优点和改进。因此,在不偏离在所附权利要求和其等价物所规定的,本发明一般概念的内容或范围内,可以进行各种修改。
Claims (17)
1.一种用于二氧化硅工件的化学机械抛光的水性无浆组合物,其包括:能在中性至碱性的pH条件下溶解和离解的阳离子表面活性剂,所述的阳离子表面活性剂以水性无浆组合物的形式存在,其含量低于其临界胶束浓度。
2.权利要求1的组合物,其中所述的低于所述临界胶束浓度的含量为低于0.1mol/l。
3.权利要求2的组合物,其中所述的阳离子表面活性剂是烷基-三甲基-卤化铵。
4.权利要求3的组合物,其中所述的烷基-三甲基-卤化铵是十六烷基-三甲基-溴化铵。
5.权利要求2的组合物,其中所述的阳离子表面活性剂是烷基-苄基-二甲基-卤化铵。
6.权利要求5的组合物,其中所述的烷基-苄基-二甲基-卤化铵选自十六烷基-苄基-二甲基溴化铵和十二烷基-苄基-二甲基-溴化铵。
7.权利要求2的组合物,其中所述的阳离子表面活性剂是吡啶烷基卤。
8.权利要求7的组合物,其中所述的吡啶烷基卤是十六烷氯化吡啶。
9.权利要求2的组合物,其中所述的阳离子表面活性剂是烷基-铵酯。
10.权利要求9的组合物,其中所述的烷基-铵酯是十二烷基铵乙酸酯。
11.权利要求2的组合物,按照所述的阳离子表面活性剂重量计算,其中外加的阴离子聚合物的存在量小于2重量%。
12.权利要求11的组合物,其中所述的阴离子聚合物选自聚丙烯酸和丙烯酸铵。
13.权利要求2的组合物,按照所述的阳离子表面活性剂重量计算,其中外加的非离子聚合物的存在量小于1重量%。
14.权利要求13的组合物,其中所述的非离子聚合物选自聚丙烯酰胺和聚乙烯醇。
15.一种减少二氧化硅工件在化学机械抛光过程中的划痕和缺陷的方法,其包括:将所述工件的表面暴露在包含阳离子表面活性剂的无浆抛光组合物中,该阳离子表面活性剂,能在中性至碱性的pH条件下溶解和离解,所述的阳离子表面活性剂在水性无浆组合物中的存在量低于其临界胶束浓度。
16.权利要求2的组合物,其中所述的阳离子表面活性剂选自烷基-三甲基-卤化铵、烷基-苄基-二甲基-卤化铵、吡啶-烷基卤、烷基铵乙酸酯、和它们的混合物,其中烷基为C6-C18。
17.权利要求2的组合物,其中所述的阳离子表面活性剂包括溴化物。
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TW471057B (en) * | 2000-06-09 | 2002-01-01 | Macronix Int Co Ltd | Method for reducing dishing effect during chemical mechanical polishing |
US6443811B1 (en) * | 2000-06-20 | 2002-09-03 | Infineon Technologies Ag | Ceria slurry solution for improved defect control of silicon dioxide chemical-mechanical polishing |
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US6800218B2 (en) | 2001-08-23 | 2004-10-05 | Advanced Technology Materials, Inc. | Abrasive free formulations for chemical mechanical polishing of copper and associated materials and method of using same |
US6677239B2 (en) * | 2001-08-24 | 2004-01-13 | Applied Materials Inc. | Methods and compositions for chemical mechanical polishing |
US20050028450A1 (en) * | 2003-08-07 | 2005-02-10 | Wen-Qing Xu | CMP slurry |
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US8431490B2 (en) * | 2010-03-31 | 2013-04-30 | Rohm And Haas Electronic Materials Cmp Holdings, Inc. | Method of chemical mechanical polishing a substrate with polishing composition adapted to enhance silicon oxide removal |
US20120295447A1 (en) * | 2010-11-24 | 2012-11-22 | Air Products And Chemicals, Inc. | Compositions and Methods for Texturing of Silicon Wafers |
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