CN113122143A - 一种化学机械抛光液及其在铜抛光中的应用 - Google Patents
一种化学机械抛光液及其在铜抛光中的应用 Download PDFInfo
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- 238000005498 polishing Methods 0.000 title claims abstract description 57
- 239000010949 copper Substances 0.000 title claims abstract description 50
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims abstract description 44
- 229910052802 copper Inorganic materials 0.000 title claims abstract description 44
- 239000000126 substance Substances 0.000 title claims abstract description 29
- 239000002245 particle Substances 0.000 claims abstract description 11
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 10
- 239000007800 oxidant agent Substances 0.000 claims description 9
- 238000000227 grinding Methods 0.000 claims description 5
- 239000002736 nonionic surfactant Substances 0.000 claims description 5
- 239000000377 silicon dioxide Substances 0.000 claims description 5
- 235000012239 silicon dioxide Nutrition 0.000 claims description 5
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical group OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 4
- 125000005233 alkylalcohol group Chemical group 0.000 claims description 4
- 125000000217 alkyl group Chemical group 0.000 claims description 2
- 125000004106 butoxy group Chemical group [*]OC([H])([H])C([H])([H])C(C([H])([H])[H])([H])[H] 0.000 claims description 2
- 125000004432 carbon atom Chemical group C* 0.000 claims description 2
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 claims description 2
- 239000007788 liquid Substances 0.000 claims description 2
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 2
- 239000006061 abrasive grain Substances 0.000 claims 1
- 229910000420 cerium oxide Inorganic materials 0.000 claims 1
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 claims 1
- 238000000034 method Methods 0.000 abstract description 17
- 239000000463 material Substances 0.000 abstract description 6
- 230000003746 surface roughness Effects 0.000 abstract description 6
- 239000003344 environmental pollutant Substances 0.000 abstract description 4
- 231100000719 pollutant Toxicity 0.000 abstract description 4
- 229910052751 metal Inorganic materials 0.000 description 5
- 239000002184 metal Substances 0.000 description 5
- 230000001590 oxidative effect Effects 0.000 description 4
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- 238000012360 testing method Methods 0.000 description 3
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 239000000356 contaminant Substances 0.000 description 2
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- 238000005516 engineering process Methods 0.000 description 2
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- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- -1 alkyl ethoxy butoxide Chemical compound 0.000 description 1
- 230000000844 anti-bacterial effect Effects 0.000 description 1
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- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 description 1
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
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- 229910021641 deionized water Inorganic materials 0.000 description 1
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- 229910017604 nitric acid Inorganic materials 0.000 description 1
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Abstract
本发明提供一种化学机械抛光液及其在铜抛光中的应用,所述化学机械抛光液包括非离子表面活性剂、研磨颗粒和氧化剂。本发明旨在提供一种可用于需去除铜基材的多种应用的化学机械抛光液,使用该化学机械抛光液可以在获得满足工艺要求的铜的去除速率的同时,降低抛光后铜表面粗糙度和铜表面污染物颗粒数,保证抛光后的铜表面质量,能够满足各种工艺条件下对铜表面的要求。
Description
技术领域
本发明涉及一种化学机械抛光液及其在铜抛光中的应用。
背景技术
在集成电路的制造过程中,硅晶圆基片上往往构建了成千上万的结构单元,这些结构单元通过多层金属互连进一步形成功能性电路和元器件。随着金属互连技术的发展和布线层数的增加,化学机械抛光(CMP)已经广泛应用于芯片制造过程中的表面平坦化。这些平坦化的芯片表面有助于多层集成电路的生产,且防止将电介层涂覆在不平表面上引起的畸变。
CMP工艺就是使用一种含磨料的混合物和抛光垫抛光集成电路表面。在典型的化学机械抛光方法中,将衬底直接与旋转抛光垫接触,用一载重物在衬底背面施加压力。在抛光期间,垫片和操作台旋转,同时在衬底背面保持向下的力,将磨料和化学活性溶液(通常称为抛光液或抛光浆料)涂于垫片上,该抛光液与正在抛光的薄膜发生化学反应开始进行抛光过程。
随着器件特征尺寸的持续减小,互连性能已成为制约芯片整体性能的关键,而制约互连性能的最大挑战就是尺寸效应造成的电阻电容延迟现象(RC delay),因此降低RC延迟成为集成电路发展中的重要内容。铜具有电阻率低、抗电迁移能率高和RC延迟时间短的优点,已经取代铝成为集成电路的主要互连金属。但由于无法对铜材进行有效的等离子蚀刻或湿法蚀刻,因而对于铜作为互连材料的布线工艺来说,目前普遍采用的技术方案就是双大马士革(Dual Damascene)镶嵌工艺,即:在第一层里形成沟槽,在沟槽内填充铜阻挡层和铜,形成金属导线并覆盖在介电层上。然后通过化学机械抛光(CMP)工艺将介电层上多余的铜/铜阻挡层除去,在沟槽里留下单个互连线。CMP技术用于铜互连工艺,使0.13μm后端铜制程变为现实,不同的工艺和制程对铜化学机械抛光液有着不同的技术要求,且随着集成电路的发展,对铜化学机械抛光工艺的要求也越来越高,不仅需要满足不同工艺和制程要求的铜的去除速率,还需要保证抛光后的铜的表面质量。铜的质地比较软,且容易发生氧化,在抛光过程中会形成由CuO、Cu2O和Cu(OH)2等构成的多孔氧化物层。所以铜比诸如二氧化硅(TEOS)等的硅材料或诸如钨的其他材料更脆弱,很容易在抛光过程中造成划痕等表面损伤。
发明内容
为解决现有技术在抛光过程中铜表面容易造成损伤,导致表面粗糙度值大和污染物残留多的问题,本发明提供一种化学机械抛光液,包括非离子表面活性剂、研磨颗粒和氧化剂。
其中,所述非离子表面活性剂为(乙氧基)x化(丁氧基)y化烷基醇,其中x为5~20,y为5~20,烷基为碳原子数为11~15的直链或支链。所述非离子表面活性剂的质量百分比浓度为0.0005~0.5wt%。优选为0.001~0.1wt%。
其中,所述研磨颗粒为二氧化硅、三氧化二铝、二氧化铈、掺杂铝的二氧化硅中的一种或多种。所述研磨颗粒的质量百分比浓度为0.1~20wt%,优选为0.1~10wt%。所述研磨颗粒的粒径为20~200nm,优选为30~120nm。
其中,所述氧化剂为过氧化氢,所述氧化剂的质量百分比浓度为0.05~5wt%。
其中,所述化学机械抛光液的pH值为4~12,优选为5~11。
本发明中的化学机械抛光液中,还可以包含pH调节剂和杀菌剂等其他本领域的添加剂。
本发明的化学机械抛光液可以浓缩制备,在使用前用去离子水稀释并添加氧化剂至本发明的浓度范围。
本发明还提供上述化学机械抛光液在铜抛光中的应用。
本申请采用的试剂均市售可得。
应当理解的是,本发明所述wt%均指的是质量百分比浓度。
与现有技术相比较,本发明的优势在于:
本发明旨在提供一种可用于铜抛光、阻挡层抛光和硅通孔(Through SiliconVia,TSV)抛光等工艺中需去除铜基材的多种应用的化学机械抛光液,使用该化学机械抛光液可以在获得满足工艺要求的铜的去除速率的同时,降低和改善抛光后铜表面粗糙度和铜表面污染物颗粒,保证抛光后的铜表面质量能够满足各种工艺条件下对铜表面的要求。
具体实施方式
下面通过实施例的方式进一步说明本发明,但并不以此将本发明限制在所述的实施例范围之中。
实施例
制备方法:按照表1中的配方,将除氧化剂以外的其他组分混合均匀,用KOH或HNO3调节到所需要的pH值。使用前加氧化剂,混合均匀即可。水为余量。
表1.对比例1~2和实施例1~11的配方
效果实施例
抛光方法:将按照表1中的配方制得的抛光液按照下述抛光条件对铜晶圆进行抛光,抛光条件:抛光机台为12”Reflexion LK机台,抛光垫为IC1010pad,下压力为1.0~3.0psi,转速为抛光盘/抛光头=93/87rpm,抛光液流速为300ml/min,抛光时间为1min。用金属薄膜测厚仪测量抛光前后的铜的电阻率,计算出抛光前后的铜的厚度,获得铜的去除速率,用原子力显微镜AFM测试的抛光后的铜晶圆表面粗糙度,用缺陷扫描仪SP2测试的抛光后的铜晶圆表面污染物颗粒数。抛光及测试结果见表2。
表2.对比例1~2和实施例1~11对Cu的去除速率、表面粗糙度、表面污染物颗粒数
如表2所示:相对于对比例1-2,本申请的实施例1-11中加入了乙氧基丁氧基化烷基醇,在不影响Cu去除速率的情况下极大的改善了抛光后Cu的表面粗糙度,并有效的减少了表面污染物的残留。从实施例4~5可看出即使在高的下压力3.0psi的抛光条件下,也能获得较好的Cu的表面质量。因而采用本发明的抛光液在获得满足工艺要求的铜去除速率的同时保证抛光后获得较好的铜表面质量,能够满足各种工艺条件下对铜表面的要求。
综上,本申请的化学机械抛光液可以在获得满足工艺要求的铜的去除速率的同时,改善和降低抛光后铜表面粗糙度和铜表面污染物颗粒数,保证抛光后的铜表面质量;且本申请的化学机械抛光液适用压力范围大,即使在较高抛光压力下,本申请的化学机械抛光液在具有高的铜去除速率的同时,也能获得较好的铜表面质量。克服了现有技术中的技术偏见。
应当注意的是,本发明中的含量,如果没有特别说明,均为质量百分比含量。
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 (9)
1.一种化学机械抛光液,其特征在于,包括非离子表面活性剂、研磨颗粒和氧化剂,其中,所述的非离子表面活性剂为(乙氧基)x化(丁氧基)y化烷基醇,其中x为5~20,y为5~20,烷基为碳原子数为11~15的直链或支链。
2.如权利要求1所述的化学机械抛光液,其特征在于,所述乙氧基化丁氧基化烷基醇的质量浓度为0.0005~0.5wt%。
3.如权利要求2所述的化学机械抛光液,其特征在于,所述乙氧基化丁氧基化烷基醇的质量浓度为0.001~0.1wt%。
4.如权利要求1所述的化学机械抛光液,其特征在于,所述研磨颗粒为二氧化硅、三氧化二铝、二氧化铈、掺杂铝的二氧化硅中的一种或多种。
5.如权利要求1所述的化学机械抛光液,其特征在于,所述研磨颗粒的质量浓度为0.1~20wt%。
6.如权利要求1所述的化学机械抛光液,其特征在于,所述氧化剂为过氧化氢。
7.如权利要求1所述的化学机械抛光液,其特征在于,所述氧化剂的质量浓度为0.05~5wt%。
8.如权利要求1所述的化学机械抛光液,其特征在于,所述化学机械抛光液的pH值为4~12。
9.一种如权利要求1-8任一所述的化学机械抛光液在铜抛光中的应用。
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