物理化学学报 >> 2017, Vol. 33 >> Issue (10): 2042-2051.doi: 10.3866/PKU.WHXB201705125

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光诱导约束刻蚀体系中的TiO2纳米管阵列光电极上Cu的沉积及抑制

黄雅钰,方秋艳,周剑章*(),詹东平,时康,田中群   

  • 收稿日期:2017-04-13 发布日期:2017-07-17
  • 通讯作者: 周剑章 E-mail:jzzhou@xmu.edu.cn
  • 基金资助:
    国家自然科学基金(91023043);国家自然科学基金(21021002);国家自然科学基金(91023006)

Deposition and Inhibition of Cu on TiO2 Nanotube Photoelectrode in Photoinduced Confined Etching System

Ya-Yu HUANG,Qiu-Yan FANG,Jian-Zhang ZHOU*(),Dong-Ping ZHAN,Kang SHI,Zhong-Qun TIAN   

  • Received:2017-04-13 Published:2017-07-17
  • Contact: Jian-Zhang ZHOU E-mail:jzzhou@xmu.edu.cn
  • Supported by:
    the National Natural Science Foundation of China(91023043);the National Natural Science Foundation of China(21021002);the National Natural Science Foundation of China(91023006)

摘要:

光诱导约束刻蚀可作为一种无应力的化学平坦化方法用于Cu的抛光。我们发现在光诱导约束刻蚀工件Cu的过程中,工具表面的TiO2纳米管上可能出现Cu沉积。通过扫描电子显微镜及其能谱,X射线光电子能谱等方法分析其沉积形貌和成分组成,探究在工具-工件之间的微纳尺度液层中Cu光催化还原沉积的机制,并在模拟液中研究Cu沉积对刻蚀体系的影响。探究引入搅拌、加入络合剂对TiO2纳米管表面Cu的沉积的抑制,并考察抑制措施对于工件Cu刻蚀的影响。结果表明Cu沉积会增强TiO2纳米管光电极的光催化性能,但随着沉积量的增加,增强机制会发生变化;在尝试抑制Cu沉积时也发现改善传质以抑制Cu沉积的同时也会带来工件Cu的刻蚀增强;采用添加络合剂结合改善传质的方法有望在抑制Cu沉积的同时提高平坦化效果。所以抑制方法和条件的选择需兼顾对工具-工件之间微纳液层中的多个化学和传质过程的影响。这些研究对于进一步优化光诱导约束刻蚀体系及其在化学平坦化中的应用有重要的指导意义。

关键词: 光诱导约束刻蚀, TiO2纳米管阵列, 羟基自由基, 约束剂, Cu的光催化沉积, 传质

Abstract:

A photoinduced confined etching system was used for the unstressed chemical planarization of Cu. Cu deposits were found on the surface of TiO2 nanotubes of the tool during the photoinduced confined etching of the Cu workpiece. Scanning electron microscopy, energy-dispersive X-ray spectroscopy, and X-ray photoelectron spectroscopy were used to analyze the morphology and composition of the Cu deposits, and the mechanism of the photodeposition of Cu in the micro/nanoscale liquid layer between the tool and the workpiece was investigated. Moreover, a simulated cupric solution was used to study the effect of the Cu deposits during the photoinduced confined etching. Several routes including stirring and complexing agent were used to investigate the inhibition of Cu deposition on the surface of TiO2 nanotubes and the simultaneous effect on the etching of Cu workpiece. The results showed that the Cu deposits enhanced the photocatalytic performance of TiO2 nanotubes, but the mechanism of enhancement changed with the increase in Cu deposits. Inhibition of Cu deposition by improving mass transfer can lead to the increase in the etching of Cu; addition of complexing agent combined with enhanced mass-transfer can inhibit Cu deposition, while improving the planing effect. Thus, the choice of inhibition methods and conditions should balance the effect of the micro/nano liquid layer between the tool and workpiece on multiple chemical reactions and mass transfer processes. The results provide an important guiding significance for further regulation and optimization of the photoinduced confined etching system.

Key words: Photo-induced confined etching, TiO2 nanotube arrays, ·OH, Scavenging agent, Photo-deposition of Cu, Mass transfer

MSC2000: 

  • O649