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绿色环保化学机械抛光液的研究进展

郜培丽 张振宇 王冬 张乐振 徐光宏 孟凡宁 谢文祥 毕胜

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绿色环保化学机械抛光液的研究进展

郜培丽, 张振宇, 王冬, 张乐振, 徐光宏, 孟凡宁, 谢文祥, 毕胜

Research progress of green chemical mechanical polishing slurry

Gao Pei-Li, Zhang Zhen-Yu, Wang Dong, Zhang Le-Zhen, Xu Guang-Hong, Meng Fan-Ning, Xie Wen-Xiang, Bi Sheng
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  • 原子级加工制造是实现半导体晶圆原子尺度超光滑表面的有效途径. 作为大尺寸高精密功能材料的原子级表面制造的重要加工手段之一, 化学机械抛光(chemical mechanical polishing, CMP)凭借化学腐蚀和机械磨削的耦合协同作用, 成为实现先进材料或器件超光滑无损伤表面平坦化加工的关键技术, 在航空、航天、微电子等众多领域得到了广泛应用. 然而, 为了实现原子层级超滑表面的制备, CMP工艺中常采用的化学腐蚀和机械磨削方法需要使用具有强烈腐蚀性和高毒性的危险化学品, 对生态系统产生了不可逆转的危害. 因此, 本文以绿色环保高性能抛光液作为对象, 对加工原子量级表面所采用的化学添加剂进行分类总结, 详尽分析在CMP过程中化学添加剂对材料表面性质调制的作用机理, 为在原子级尺度下改善表面性质提供可参考的依据. 最后, 提出了CMP抛光液在原子级加工研究中面临的挑战, 并对未来抛光液发展方向作出了展望, 这对原子尺度表面精度的进一步提升具有深远的现实意义.
    Atomic-scale fabrication is an effective way to realize the ultra-smooth surfaces of semiconductor wafers on an atomic scale. As one of the crucial manufacturing means for atomically precise surface of large-sized functional materials, chemical mechanical polishing (CMP) has become a key technology for ultra-smooth and non-damage surface planarization of advanced materials and devices by virtue of the synergetic effect of chemical corrosion and mechanical grinding. It has been widely used in aviation, aerospace, microelectronics, and many other fields. However, in order to achieve ultra-smooth surface processing at an atomic level, chemical corrosion and mechanical grinding methods commonly used in CMP process require some highly corrosive and toxic hazardous chemicals, which would cause irreversible damage to the ecosystems. Therefore, the recently reported green chemical additives used in high-performance and environmentally friendly CMP slurry for processing atomically precise surface are summarized here in this paper. Moreover, the mechanism of chemical reagents to the modulation of materials surface properties in the CMP process is also analyzed in detail. This will provide a reference for improving the surface characteristics on an atomic scale. Finally, the challenges that the polishing slurry is facing in the research of atomic-scale processing are put forward, and their future development directions are prospected too, which has profound practical significance for further improving the atomic-scale surface accuracy.
      通信作者: 张振宇, zzy@dlut.edu.cn
    • 基金项目: 国家重点研发计划(批准号: 2018YFA0703400)资助的课题
      Corresponding author: Zhang Zhen-Yu, zzy@dlut.edu.cn
    • Funds: Project supported by the National Key R&D Program of China (Grant No. 2018YFA0703400)
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  • 图 1  CMP系统示意图

    Fig. 1.  Diagram of CMP system.

    图 2  不同H2O2浓度下铝合金基底的氧化和腐蚀过程示意图[37]

    Fig. 2.  Schematic diagram for the oxidation and corrosion processes of substrates with various H2O2 concentration[37].

    图 3  (a) 利用臭氧气体发生器产生的含气泡的强化浆料对SiC衬底的CMP方法示意图[48]; (b) 基于电芬顿反应的6H-SiC单晶增强CMP法原理图[49]; (c) 氯化钠水溶液阳极氧化装置示意图[50]; (d) 光化学辅助CMP示意图[51]

    Fig. 3.  (a) Illustration of proposed CMP method of SiC substrate by enhanced slurry containing bubbles enclosing ozone gas generated by ozone gas generator[48]; (b) schematic diagram of enhanced CMP method for single-crystal 6H-SiC based on electro-Fenton reaction[49]; (c) schematic diagram of anodic oxidation setup with sodium chloride aqueous solution[50]; (d) schematic diagram of photochemically combined CMP process[51].

    图 4  研制的优化CMP浆料的CMP机理示意图[29]

    Fig. 4.  Schematic diagram of the CMP mechanism for the developed optimal CMP slurry[29].

    图 5  (a) 具有阻挡层的Cu互连线的抛光过程; (b) CMP加工后具有的典型的碟状结构图形[70]; (c) 电偶腐蚀的示意图[71]

    Fig. 5.  (a) Schematic of the CMP process of Cu interconnect with a barrier; (b) typical dishing profiles of the pattern feature after CMP process[70]; (c) schematic diagram of galvanic corrosion[71].

    图 6  离子(a)和非离子(b)表面活性剂对高离子强度泥浆稳定性的影响; (c) 阴离子和非离子表面活性剂协同混合的高离子强度浆料稳定机理[102]

    Fig. 6.  Effects of ionic (a) and nonionic (b) surfactant addition on the stability of high ionic strength slurries; (c) mechanism of high ionic strength slurry stabilization by the synergistic mixture of anionic and nonionic surfactants[102].

    图 7  表面活性剂在液-汽界面和液-固界面的分布示意图 (a) 阳离子表面活性剂; (b) 非离子表面活性剂; (c) 阴离子表面活性剂[103]

    Fig. 7.  Schematics of how the surfactants are partitioned on the liquid-vapor and liquid-solid interfaces: (a) Cationic surfactants; (b) nonionic surfactants; (c) anionic surfactants[103]

    图 8  (a) 污染的图案化晶圆SEM图像(左)以及污染(中间)和清洁(右)的晶圆表面缺陷图[107]; (b) 污染(左)和清洁(右)的铜样品AFM图像[88]

    Fig. 8.  (a) SEM images (left) of contaminated patterned wafer and the defect map on contaminated (centre) and cleaned (right) wafer surface[107]; (b) AFM images of contaminated (left) and cleaned (right) Cu sample[88].

  • [1]

    Liao Z R, Abdelhafeez A, Li H N, Yang Y, Diaz O Z, Axinte D 2019 Int. J. Mach. Tools Manuf. 143 63Google Scholar

    [2]

    Chappert C, Bernas H, Ferre J, Kottler V, Jamet J P, Chen Y, Cambril E, Devolder T, Rousseaux F, Mathet V, Launois H 1998 Science 280 1919Google Scholar

    [3]

    Krishnan M, Nalaskowski J W, Cook L M 2010 Chem. Rev. 110 178Google Scholar

    [4]

    Zhong Z W 2020 Int. J. Adv. Manuf. Technol. 109 1419Google Scholar

    [5]

    Frank B, Kahl P, Podbiel D, Spektor G, Orenstein M, Fu L, Weiss T, Hoegen M H, Davis T J, zu Heringdorf F J M 2017 Sci. Adv. 3 1700721Google Scholar

    [6]

    Nagpal P, Lindquist N C, Oh S H, Norris D J 2009 Science 325 594Google Scholar

    [7]

    Zhang S J, Zhou Y P, Zhang H J, Xiong Z W, To S 2019 Int. J. Mach. Tools Manuf. 142 16Google Scholar

    [8]

    Guo X G, Yuan S, Huang J X, Chen C, Kang R K, Jin Z J, Guo D M 2020 Appl. Surf. Sci. 505 144610Google Scholar

    [9]

    Yuan S, Guo X G, Huang J X, Gou Y J, Jin Z J, Kang R K, Guo D M 2020 Tribol. Int. 148 106308Google Scholar

    [10]

    Qin C J, Hu Z H, Tang A M, Yang Z P, Luo S 2020 Wear 452–453 203293Google Scholar

    [11]

    Zhang Z F, Yan W X, Zhang L, Liu W L, Song Z T 2011 Microelectron. Eng. 88 3020Google Scholar

    [12]

    Xu W H, Cheng Y Y, Zhong M 2019 Microelectron. Eng. 216 111029Google Scholar

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出版历程
  • 收稿日期:  2020-11-14
  • 修回日期:  2020-12-30
  • 上网日期:  2021-03-11
  • 刊出日期:  2021-03-20

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