CN1429930A - 用于钌的化学机械抛光的溶液 - Google Patents
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Abstract
本发明公开了一种用于钌的化学机械抛光的溶液，其包含硝酸和氧化剂。还公开了用抛光的钌层来形成钌图案的方法。所公开的溶液提高了低抛光压力下钌的抛光速度，减少了钌的表面凹陷，并且降低了在层间绝缘薄膜中产生的划痕。因此，所公开的溶液和方法可以改进了装置隔离的技术，并减少覆盖的步骤。
Description
技术领域
本发明涉及一种用于钌的化学机械抛光(简称“CMP”)的溶液，其包含硝酸和氧化剂。具体地，本发明涉及一种利用上述的钌CMP溶液进行的包括CMP处理的钌图案成型方法。
背景技术
钌是化学上和机械上均稳定的贵金属，而且是制备高性能半导体装置的基本材料。另外，钌最近已被用作形成DRAM部件中金属层/绝缘薄膜/金属层型电容器中的低电极(lower electrode)。
但是，在CMP工艺中不能提供适宜的CMP浆液以抛光钌，因为钌的反应性较低。因此，在抛光钌时采用用于其它金属如钨或铝的浆液。
用于其它金属的浆液包括用于抛光硅基材上各种金属层的化学品。一般地，用于金属CMP工艺且具有pH为2～4的强酸性的浆液包含氧化剂如过氧化氢(H2O2)或硝酸铁(Fe(NO3)3)以及研磨剂如氧化铝(Al2O3)或二氧化锰(MnO2)。另外，还可以添加少量的表面活性剂，以改善CMP浆液的性能。
钌的抛光速度非常慢，所以CMP工艺需要在高抛光压力下进行很长时间，以便使钌得到充分的抛光。
结果，钌层可能与层间的绝缘薄膜分离，因为钌层对层间的绝缘薄膜具有较差的附着力。另外，与层间绝缘薄膜相邻的钌层上产生凹陷和腐蚀作用。
此外，长时间在高抛光压力下抛光钌时，浆液中的研磨剂可能严重地划伤层间的绝缘薄膜，而且产生如浆液沉淀等杂质并且保留在后来的浆液中。因此，损害所得装置的性能。
发明内容
本发明公开一种用于钌CMP的溶液，其可以在低抛光压力下提高钌的抛光速度，并降低钌层的表面凹陷和层间绝缘薄膜的划痕。
本发明还公开了利用上述溶液进行包括CMP工艺的金属图案成型方法。
附图说明
图1是利用所公开的溶液进行钌-CMP工艺之前由钌成型的金属图案的横断面图。
图2是利用所公开的溶液进行钌-CMP工艺之后的金属图案的前视图。
图3是利用所公开的溶液进行钌-CMP工艺之后除去了钌的金属图案的横断面图。
具体实施方式
本发明公开了一种含有硝酸和氧化剂的CMP溶液。
该CMP溶液用于钌的抛光和平整。
优选硝酸的浓度为约0.01～10M，更优选为约0.01～5M，而且优选pH为约1～5，更优选pH为约1～3。当硝酸的浓度小于0.1M时，氧化剂如硝酸铈铵[(NH4)2Ce(NO3)6]的性能降低。
一种优选的氧化钌的氧化剂为硝酸铈铵，其在硝酸中的浓度为约0.01～10M，优选为约0.01～5M。
优选含有硝酸的CMP溶液保持其pH为约1～5，更优选为约1～3，甚至在其中添加了氧化剂时。
钌CMP溶液借助于硝酸与适宜氧化剂的组合改变了钌层表面的物理和化学性质。
换言之，利用所公开的CMP溶液，钌原子间的结合强度和紧密度降低，钌层表面的腐蚀和溶解速度增加，在相同压力下的抛光速度提高，导致钌层容易平整化。
另外，与常规的浆液相比，该钌CMP溶液不包括研磨剂，所以可以降低在层间绝缘薄膜中产生的划痕。
下面将描述制备所公开的钌CMP溶液的方法。首先，制备0.01～10M的硝酸，然后向其中加入硝酸铈铵并搅拌，使硝酸铈铵的浓度为0.01～10M。
其后，进一步搅拌所得的混合物约30分钟，以使其完全混合并稳定化。
利用所公开的钌CMP溶液进行钌图案成型的方法包括：
(a)在半导体基材上形成具有接触孔的层间绝缘薄膜图案；
(b)在层间绝缘薄膜图案上形成钌层；和
(c)利用所公开的溶液对钌层的整个表面进行钌CMP处理。
步骤(c)可以进一步包括利用层间绝缘薄膜的抛光浆液对步骤(c)的产物进行接触型抛光处理。
在第一CMP工艺中，由钌构成的半导体基材在压力下与形成于CMP系统转盘上的抛光垫接触。
然后向抛光垫与钌层的界面上供给所公开的钌CMP溶液，并对钌层进行抛光。
CMP工艺是在约1～3psi的压力下，旋转型系统的转盘转速为约10～80rpm，且转盘的线性速度为约100～600 fpm的情况下进行的，这取决于钌层的抛光速度和层间绝缘薄膜的抛光性质。
在第二抛光工艺中，在层间绝缘薄膜暴露时，利用层间绝缘薄膜的CMP浆液对层间绝缘薄膜进行接触抛光。接触抛光是为了防止因钌层与层间绝缘薄膜之间的抛光选择性差异而产生的钌层表面凹陷而进行的缓冲步骤。
在上述CMP工艺中可以根据钌层的抛光性质选用不同类型的抛光垫。例如，可以使用柔软的抛光垫，以提高抛光层的均匀性，也可以使用硬质抛光垫，以提高抛光层的平面性。此外，还可以使用上述两种抛光垫层压起来的层叠垫或者上述抛光垫的组合。
另外，可以在形成钌层之前于层间绝缘薄膜的顶面上形成金属附着层，如钛(Ti)层或者氮化钛(TiN)层，以便提高钌的附着性(见图1)。
也就是说，形成钌图案的方法可以包括：
(a)在半导体基材上形成具有接触孔的层间绝缘薄膜图案；
(b)在层间绝缘薄膜图案上形成金属附着层；
(c)在金属附着层上形成钌层；
(d)利用所公开的溶液对钌层的整个表面进行钌CMP处理，直到露出金属附着层为止；
(e)利用金属浆液对所得的表面进行CMP处理，直到层间绝缘薄膜暴露出来为止；和
(f)用层间绝缘薄膜的抛光浆液对生成的表面进行接触抛光处理。
优选层间绝缘图案为氧化物图案，并使用钌图案作为低电极图案。
在第一CMP工艺中，由钌构成的半导体基材在压力下与形成于CMP系统转盘上的抛光垫接触。
然后，向抛光垫与钌层的界面上供给所公开的钌CMP溶液，并对钌层进行抛光。
CMP工艺是在约1～3psi的压力下，旋转型系统的转盘转速为约10～80rpm，且转盘的线性速度为约100～600 fpm的情况下进行的，这取决于钌层的抛光速度和层间绝缘薄膜的抛光性质。
在第二抛光工艺中，对金属附着层进行抛光(见图2)。
在第三抛光工艺中，在层间绝缘薄膜暴露时，利用层间绝缘薄膜的CMP浆液对层间绝缘薄膜进行接触抛光(见图3)。接触抛光是为了防止因金属附着层与层间绝缘薄膜之间的抛光选择性差异而产生的钌层表面凹陷而进行的缓冲步骤。
可以使用通用的抛光浆液作为上述用于金属和氧化物薄膜的CMP浆液。
如前所述，所公开的CMP工艺是利用所公开的在硝酸中含有硝酸铈铵的钌CMP溶液进行的，其可以提高低抛光压力下钌的抛光速度，并且减少钌层的表面凹陷。
另外，所公开的溶液可以降低在层间绝缘薄膜中产生的划痕，因为该溶液不包含研磨剂。
因此可以改进装置分离的技术并减少覆盖的步骤。
Claims (16)
1.一种包含硝酸和氧化剂的CMP溶液。
2.根据权利要求1的溶液，其中该CMP溶液用于钌的抛光。
3.根据权利要求1的溶液，其中所述硝酸的浓度范围为约0.01～10M。
4.根据权利要求3的溶液，其中该硝酸的浓度范围为约0.01～5M。
5.根据权利要求1的溶液，其中该溶液的pH范围为约1～5。
6.根据权利要求5的溶液，其中该溶液的pH范围为约1～3。
7.根据权利要求1的溶液，其中所述氧化剂为硝酸铈铵[(NH4)2Ce(NO3)6]。
8.根据权利要求1的溶液，其中所述氧化剂的浓度为约0.01～10M。
9.根据权利要求8的溶液，其中该氧化剂的浓度为约0.01～5M。
10.一种形成钌图案的方法，包括：
(a)在半导体基材上形成具有接触孔的层间绝缘薄膜图案；
(b)在层间绝缘薄膜图案上形成钌层；和
(c)利用权利要求1的CMP溶液对钌层的整个表面进行钌的CMP处理。
11.根据权利要求10的方法，进一步包括在步骤(c)之后，利用层间绝缘薄膜的抛光浆液对步骤(c)的产物进行接触性抛光处理。
12.根据权利要求10的方法，其中该层间绝缘薄膜图案为氧化物图案。
13.根据权利要求10的方法，其中使用该钌图案作为低电极图案。
14.一种形成钌图案的方法，包括：
(a)在半导体基材上形成具有接触孔的层间绝缘薄膜图案；
(b)在层间绝缘薄膜图案上形成金属附着层；
(c)在金属附着层上形成钌层；
(d)利用权利要求1的CMP溶液对钌层的整个表面进行钌CMP处理，直到露出金属附着层为止；
(e)利用金属浆液对所得的表面进行CMP处理，直到层间绝缘薄膜暴露出来为止；和
(f)利用层间绝缘薄膜的抛光浆液对所得的表面进行接触抛光处理。
15.根据权利要求14的方法，其中该层间绝缘薄膜图案为氧化物图案。
16.根据权利要求14的方法，其中使用该钌图案作为低电极图案。
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| KR88302/2001 | 2001-12-29 | ||
| KR10-2001-0088302A KR100444308B1 (ko) | 2001-12-29 | 2001-12-29 | 반도체 소자의 형성 방법 |
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| CN1429930A true CN1429930A (zh) | 2003-07-16 |
| CN1215199C CN1215199C (zh) | 2005-08-17 |
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| CNB021590451A Expired - Fee Related CN1215199C (zh) | 2001-12-29 | 2002-12-27 | 用于钌的化学机械抛光的溶液 |
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| US (1) | US6797624B2 (zh) |
| JP (1) | JP4756814B2 (zh) |
| KR (1) | KR100444308B1 (zh) |
| CN (1) | CN1215199C (zh) |
| TW (1) | TW593610B (zh) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104576351A (zh) * | 2013-10-23 | 2015-04-29 | 中芯国际集成电路制造(上海)有限公司 | 化学机械研磨方法 |
| CN113897611A (zh) * | 2020-06-22 | 2022-01-07 | 国核锆铪理化检测有限公司 | 一种含钌锆合金腐蚀剂及腐蚀方法 |
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| US7513920B2 (en) * | 2002-02-11 | 2009-04-07 | Dupont Air Products Nanomaterials Llc | Free radical-forming activator attached to solid and used to enhance CMP formulations |
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| US20060200489A1 (en) * | 2005-03-03 | 2006-09-07 | Microsoft Corporation | Company modeling |
| US7900152B2 (en) * | 2005-03-03 | 2011-03-01 | Microsoft Corporation | Adaptable user interface for business software |
| US7917555B2 (en) * | 2005-03-03 | 2011-03-29 | Microsoft Corporation | Creating, storing and viewing process models |
| US7476620B2 (en) * | 2005-03-25 | 2009-01-13 | Dupont Air Products Nanomaterials Llc | Dihydroxy enol compounds used in chemical mechanical polishing compositions having metal ion oxidizers |
| US8008202B2 (en) * | 2007-08-01 | 2011-08-30 | Cabot Microelectronics Corporation | Ruthenium CMP compositions and methods |
| US20100096584A1 (en) * | 2008-10-22 | 2010-04-22 | Fujimi Corporation | Polishing Composition and Polishing Method Using the Same |
| KR200454347Y1 (ko) * | 2008-12-24 | 2011-06-29 | 이랄라 | 사진인쇄용 시트 |
| US9196283B1 (en) | 2013-03-13 | 2015-11-24 | Western Digital (Fremont), Llc | Method for providing a magnetic recording transducer using a chemical buffer |
| US11820919B2 (en) | 2021-10-19 | 2023-11-21 | Tokyo Electron Limited | Ruthenium CMP chemistry based on halogenation |
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| KR19980019046A (ko) * | 1996-08-29 | 1998-06-05 | 고사이 아키오 | 연마용 조성물 및 이의 용도(Abrasive composition and use of the same) |
| JPH11121411A (ja) * | 1997-10-09 | 1999-04-30 | Matsushita Electron Corp | 研磨用スラリー，白金族系金属膜の研磨方法及び半導体記憶装置のセル形成方法 |
| JP2000038573A (ja) * | 1998-05-19 | 2000-02-08 | Showa Denko Kk | 半導体装置用金属膜研磨スラリ― |
| JP3660511B2 (ja) * | 1998-12-03 | 2005-06-15 | 株式会社東芝 | 研磨方法及び半導体装置の製造方法 |
| KR100472882B1 (ko) * | 1999-01-18 | 2005-03-07 | 가부시끼가이샤 도시바 | 수계 분산체, 이를 이용한 화학 기계 연마용 수계 분산체조성물, 웨이퍼 표면의 연마 방법 및 반도체 장치의 제조방법 |
| US6355153B1 (en) * | 1999-09-17 | 2002-03-12 | Nutool, Inc. | Chip interconnect and packaging deposition methods and structures |
| JP2001115144A (ja) * | 1999-10-15 | 2001-04-24 | Hitachi Chem Co Ltd | 研磨材、基板の研磨方法及び半導体装置 |
| KR100529381B1 (ko) * | 1999-11-05 | 2005-11-17 | 주식회사 하이닉스반도체 | 전면식각 및 연마를 이용한 반도체 소자의 캐패시터하부전극 형성 방법 |
| JP3805588B2 (ja) * | 1999-12-27 | 2006-08-02 | 株式会社日立製作所 | 半導体装置の製造方法 |
| KR20010061490A (ko) * | 1999-12-28 | 2001-07-07 | 박종섭 | 접착력 저하에 따른 하부전극의 손실을 방지할 수 있는반도체 소자의 캐패시터 하부전극 형성 방법 |
| TWI296006B (zh) * | 2000-02-09 | 2008-04-21 | Jsr Corp | |
| WO2001078116A2 (en) * | 2000-04-11 | 2001-10-18 | Cabot Microelectronics Corporation | System for the preferential removal of silicon oxide |
| JP3993369B2 (ja) * | 2000-07-14 | 2007-10-17 | 株式会社東芝 | 半導体装置の製造方法 |
| KR100535074B1 (ko) * | 2001-06-26 | 2005-12-07 | 주식회사 하이닉스반도체 | 루테늄의 화학 기계적 연마용 슬러리 및 이를 이용한연마공정 |
| US20030003747A1 (en) * | 2001-06-29 | 2003-01-02 | Jae Hong Kim | Chemical mechanical polishing slurry for ruthenium titanium nitride and polishing process using the same |
-
2001
- 2001-12-29 KR KR10-2001-0088302A patent/KR100444308B1/ko not_active IP Right Cessation
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- 2002-10-25 TW TW091125073A patent/TW593610B/zh not_active IP Right Cessation
- 2002-11-05 US US10/288,058 patent/US6797624B2/en not_active Expired - Fee Related
- 2002-12-19 JP JP2002368510A patent/JP4756814B2/ja not_active Expired - Fee Related
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104576351A (zh) * | 2013-10-23 | 2015-04-29 | 中芯国际集成电路制造(上海)有限公司 | 化学机械研磨方法 |
| CN104576351B (zh) * | 2013-10-23 | 2017-09-22 | 中芯国际集成电路制造(上海)有限公司 | 化学机械研磨方法 |
| CN113897611A (zh) * | 2020-06-22 | 2022-01-07 | 国核锆铪理化检测有限公司 | 一种含钌锆合金腐蚀剂及腐蚀方法 |
| CN113897611B (zh) * | 2020-06-22 | 2024-01-09 | 国核锆铪理化检测有限公司 | 一种含钌锆合金腐蚀剂及腐蚀方法 |
Also Published As
| Publication number | Publication date |
|---|---|
| KR20030059441A (ko) | 2003-07-10 |
| TW593610B (en) | 2004-06-21 |
| US20030124867A1 (en) | 2003-07-03 |
| KR100444308B1 (ko) | 2004-08-16 |
| JP4756814B2 (ja) | 2011-08-24 |
| US6797624B2 (en) | 2004-09-28 |
| CN1215199C (zh) | 2005-08-17 |
| JP2003218067A (ja) | 2003-07-31 |
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