CN113122147A - 一种化学机械抛光液及其使用方法 - Google Patents
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- ABLZXFCXXLZCGV-UHFFFAOYSA-N Phosphorous acid Chemical compound OP(O)=O ABLZXFCXXLZCGV-UHFFFAOYSA-N 0.000 claims abstract description 16
- 230000001590 oxidative effect Effects 0.000 claims abstract description 6
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- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 claims description 6
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 claims description 4
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 claims description 4
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 4
- 239000004408 titanium dioxide Substances 0.000 claims description 4
- 239000002131 composite material Substances 0.000 claims description 3
- 239000012286 potassium permanganate Substances 0.000 claims description 3
- BAERPNBPLZWCES-UHFFFAOYSA-N (2-hydroxy-1-phosphonoethyl)phosphonic acid Chemical compound OCC(P(O)(O)=O)P(O)(O)=O BAERPNBPLZWCES-UHFFFAOYSA-N 0.000 claims description 2
- 229940120146 EDTMP Drugs 0.000 claims description 2
- YDONNITUKPKTIG-UHFFFAOYSA-N [Nitrilotris(methylene)]trisphosphonic acid Chemical compound OP(O)(=O)CN(CP(O)(O)=O)CP(O)(O)=O YDONNITUKPKTIG-UHFFFAOYSA-N 0.000 claims description 2
- 239000006061 abrasive grain Substances 0.000 claims description 2
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- 229940090960 diethylenetriamine pentamethylene phosphonic acid Drugs 0.000 claims description 2
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- -1 methylene phosphonic acid Chemical compound 0.000 claims description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims 3
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- 239000004721 Polyphenylene oxide Substances 0.000 claims 1
- 229920000570 polyether Polymers 0.000 claims 1
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- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
- H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic Table or AIIIBV compounds with or without impurities, e.g. doping materials
- H01L21/30—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26
- H01L21/302—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26 to change their surface-physical characteristics or shape, e.g. etching, polishing, cutting
- H01L21/306—Chemical or electrical treatment, e.g. electrolytic etching
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- H—ELECTRICITY
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- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
- H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic Table or AIIIBV compounds with or without impurities, e.g. doping materials
- H01L21/30—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26
- H01L21/302—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26 to change their surface-physical characteristics or shape, e.g. etching, polishing, cutting
- H01L21/306—Chemical or electrical treatment, e.g. electrolytic etching
- H01L21/30625—With simultaneous mechanical treatment, e.g. mechanico-chemical polishing
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Abstract
本发明旨在提供一种用于含碳材料的抛光液及其使用方法。所述化学机械抛光液,包含磨料、氧化剂和有机膦酸,该抛光液在维持较高的含碳材料去除速率的同时,避免抛光过程的副产物在抛光垫上沉积,延长了抛光垫的使用寿命,降低了抛光后晶圆表面的缺陷。
Description
技术领域
本发明涉及化学机械抛光领域,尤其涉及一种化学机械抛光液及其使用方法。
背景技术
随着半导体技术的不断发展,以及大规模集成电路互连层的不断增加,导电层和绝缘介质层的平坦化技术变得尤为关键。二十世纪80年代,由IBM公司首创的化学机械抛光(CMP)技术被认为是目前全局平坦化的最有效的方法。化学机械抛光(CMP)由化学作用、机械作用以及这两种作用结合而成。它通常由一个带有抛光垫的研磨台,及一个用于承载芯片的研磨头组成。其中研磨头固定住芯片,然后将芯片的正面压在抛光垫上。当进行化学机械抛光时,研磨头在抛光垫上线性移动或是沿着与研磨台相同的运动方向旋转。与此同时,含有研磨剂的浆液被滴到抛光垫上,并因离心作用平铺在抛光垫上。芯片表面在机械和化学的双重作用下实现全局平坦化。
碳化硅、无定形碳等含碳材料作为新一代宽带隙半导体材料,具有宽带隙、高热导率、高临界击穿电场、高电子饱和迁移速率、高化学稳定性等特点,在高温、高频、大功率、高密度集成电子器件等方面具有巨大的应用潜力。然而含碳材料在常温下非常稳定,不易发生化学反应,对机械力研磨的耐受性很好,因此常用的化学机械抛光液在抛光含碳材料时,难以获得较高的抛光速度。
通常需要用氧化剂将含碳材料氧化后去除。常用的氧化剂为双氧水,但双氧水的氧化能力较弱,无法获得理想的去除速率。CN102464944A在抛光液中添加高锰酸、锰酸及其盐类等强氧化剂来提高含碳材料的化学机械抛光速率。在使用高锰酸、锰酸及其盐类作为氧化剂对含碳材料抛光过程中,由于高锰酸、锰酸等氧化剂被还原后会不可避免地生成颜色较深的副产物,而且容易沉积在抛光垫的表面和孔洞中,从而造成抛光副产物在抛光垫上的聚集,影响抛光垫寿命,而且导致抛光后的表面缺陷增加。
发明内容
为了解决上述问题,本发明提供一种抛光液及其使用方法,通过在抛光液中加入有机膦酸,在较少影响去除速率的情况下,使得抛光过程副产物可以直接和有机膦酸发生反应,形成可溶性的锰络合物,从而避免抛光过程的副产物在抛光垫上沉积,延长了抛光垫的使用寿命,同时降低了抛光后晶圆表面的缺陷。
具体的,本发明中的化学机械抛光液包含磨料、氧化剂和有机膦酸,其中,有机膦酸选自氨基三亚甲基膦酸、羟基亚乙基二膦酸、2-羟基膦酸基乙酸、亚乙基二胺四亚甲基膦酸、多氨基多醚基亚甲基膦酸和/或二乙烯三胺五亚甲基膦酸中的一种或多种;所述氧化剂为高锰酸钾。
所述磨料选自二氧化锰、三氧化二铝、二氧化铈、二氧化钛单组分磨料以及表面包覆二氧化锰、三氧化二铝、二氧化铈、二氧化钛的复合磨料中一种或多种。
本发明中,所述磨料的质量百分比浓度为0.1~10%。
本发明中,所述磨粒的粒径范围为50~500nm。
本发明中,所述氧化剂的质量百分比浓度为0.01~1%。
本发明中,所述有机膦酸的质量百分比浓度为0.01~2%,优选为0.1~0.5%。
本发明中,所述化学机械抛光液的pH值为2~6。
本发明的抛光液可以将除氧化剂以外的组分浓缩配置,使用前用去离子水稀释并加入氧化剂至本发明的浓度范围。
另一方面,本发明提供了一种本发明中化学机械抛光液的使用方法,包括:将本发明的化学机械抛光液用于含碳材料的化学机械抛光。
与现有技术相比较,本发明的优势在于:在所述化学机械抛光液中加入有机膦酸,减少了抛光后的副产物残留,同时降低了抛光后晶圆表面的缺陷。
具体实施方式
下面结合具体实施例,详细阐述本发明的优势。
根据表1中所给配方,配置本申请对比例1~4与实施例1~23的抛光液,随后将一定浓度的氧化剂溶液、有机膦酸与研磨颗粒混合均匀,用水补足质量百分比至100%,使用KOH或HNO3将抛光液调节至所需pH值即可。
表1对比例1~4和实施例1~23的抛光液成分、含量及其pH
效果实施例1
采用对比例1~4和实施例15~23的抛光液,按照下述条件对空片无定形碳进行抛光。具体抛光条件:抛光机台为Reflexion LK,抛光垫IC1010抛光垫,300mm晶圆,研磨压力2.5psi,研磨盘转速93转/分钟,研磨头转速87转/分钟,抛光液流速为300ml/min,抛光时间为1min。测得对比例1~4和实施例15~23的抛光效果数据记于表2。
表2对比例1~4和实施例15~23的抛光效果数据
其中抛光垫表面清洁程度按以下方式进行描述:
++++抛光垫表面有严重污染;+++抛光垫表面有明显污染;++抛光垫表面有少量污染;+抛光垫表面无明显污染。
由表2可见,与对比例相比,本发明实施例的抛光液具有较高的无定形碳去除速率。对比例1~3的抛光液含有单组分的研磨颗粒,对比例4抛光液选用了复合研磨颗粒和高锰酸钾作为氧化剂,具有一定的无定形碳的去除速率,但抛光后抛光垫表面清洁程度较差。与对比例2、3和4的抛光液相比,实施例15、16和18的抛光液添加了有机膦酸,其无定形碳的去除速率略有降低,但能够抑制抛光副产物的生成,减少抛光垫表面的污染,抛光垫表面清洁程度显著提升。
由此可见,本发明的实施例15~23抛光液通过选择合适的粒径的研磨颗粒、氧化剂及有机膦酸,并调节合适的pH值,在保证较高的无定形碳去除速率的同时,减少抛光副产物,在抛光垫表面清洁程度显著改善。
效果实施例2
采用对比例1~4和本发明实施例20~23的抛光液,按照下述条件对空片无定形碳进行抛光并检测表面缺陷数量。具体抛光条件:
抛光条件:抛光机台为Reflexion LK,抛光垫IC1010抛光垫,300mm晶圆,研磨压力2.5psi,研磨盘转速93转/分钟,研磨头转速87转/分钟,抛光液流速为300ml/min,抛光时间为1min。用表面缺陷扫描仪SP2检测抛光后空白晶圆的表面缺陷数,所得的表面缺陷数的结果列于表3。
表3对比例1~4和实施例20~23的抛光后无定形碳表面缺陷数
抛光液 | 无定形碳表面缺陷数(>80nm)(颗) |
对比例1 | 396 |
对比例2 | 419 |
对比例3 | 387 |
对比例4 | 425 |
实施例20 | 66 |
实施例21 | 52 |
实施例22 | 33 |
实施例23 | 47 |
由表3可见,对比例1~4未使用有机膦酸,抛光后无定形碳晶圆表面的缺陷数量450~450颗的范围内,而在本发明中使用有机膦酸的实施例20~23的抛光液对抛光后无定形碳表面缺陷有显著改善,表面缺陷数量减少至30~70颗的范围内,无定形碳表面缺陷数量大幅度降低。
效果实施例3
采用对比例1~4和实施例20~23的抛光液,按照下述条件对空片碳化硅进行抛光。具体抛光条件:抛光机台为Reflexion LK,抛光垫IC1010抛光垫,300mm晶圆,研磨压力2.5psi,研磨盘转速93转/分钟,研磨头转速87转/分钟,抛光液流速为300ml/min,抛光时间为1min。测得对比例1~4和实施例20~23的抛光效果数据记于表4。
表4对比例1~4和实施例20~23的碳化硅抛光效果数据
抛光液 | 碳化硅去除速率(A/min) | 抛光垫表面清洁程度 |
对比例1 | 220 | +++ |
对比例2 | 674 | +++ |
对比例3 | 281 | ++++ |
对比例4 | 659 | +++ |
实施例20 | 782 | ++ |
实施例21 | 728 | + |
实施例22 | 663 | + |
实施例23 | 679 | + |
由表4可见,与未添加有机膦酸的对比例1~4相比,本发明使用有机膦酸的实施例20~23的抛光液,仍有较高的碳化硅的去除速率,同时抑制抛光副产物的生成,减少抛光垫表面的污染,提高抛光垫表面清洁程度。
综上所述,本发明通过添加有机膦酸,在酸性条件下保证抛光液对含碳材料具有较高的去除速率,减少抛光后的副产物残留,同时降低抛光后晶圆表面的缺陷。
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,包含磨料、氧化剂和有机膦酸,其特征在于,
所述有机膦酸选自氨基三亚甲基膦酸、羟基亚乙基二膦酸、2-羟基膦酸基乙酸、亚乙基二胺四亚甲基膦酸、多氨基多醚基亚甲基膦酸和/或二乙烯三胺五亚甲基膦酸中的一种或多种;
所述氧化剂为高锰酸钾。
2.如权利要求1所述的化学机械抛光液,其特征在于,
所述磨料选自二氧化锰、三氧化二铝、二氧化铈、二氧化钛单组分磨料以及表面包覆二氧化硅、三氧化二铝、二氧化铈、二氧化钛的复合磨料中一种或多种。
3.如权利要求1所述的化学机械抛光液,其特征在于,
所述磨料的质量百分比浓度为0.1~10%。
4.如权利要求1所述的化学机械抛光液,其特征在于,
所述磨粒的粒径范围为50~500nm。
5.如权利要求1所述的化学机械抛光液,其特征在于,
所述氧化剂的质量百分比浓度为0.01~1%。
6.如权利要求1所述的化学机械抛光液,其特征在于,
所述有机膦酸的质量百分比浓度为0.01~2%。
7.如权利要求6所述的化学机械抛光液,其特征在于,
所述有机膦酸的质量百分比浓度为0.1~0.5%。
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2~6。
9.一种化学机械抛光液的使用方法,其特征在于,
将如权利要求1~8中任一项所述的化学机械抛光液用于含碳材料的化学机械抛光。
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