Shell-Isolated Tip-Enhanced Raman and Fluorescence Spectroscopy. 2018

Ya-Ping Huang, and Sheng-Chao Huang, and Xiang-Jie Wang, and Nataraju Bodappa, and Chao-Yu Li, and Hao Yin, and Hai-Sheng Su, and Meng Meng, and Hua Zhang, and Bin Ren, and Zhi-Lin Yang, and Renato Zenobi, and Zhong-Qun Tian, and Jian-Feng Li
MOE Key Laboratory of Spectrochemical Analysis and Instrumentation, State Key Laboratory of Physical Chemistry of Solid Surfaces,iChEM, College of Chemistry and Chemical Engineering, Xiamen University, Xiamen, 361005, China.

Tip-enhanced Raman spectroscopy can provide molecular fingerprint information with ultrahigh spatial resolution, but the tip will be easily contaminated, thus leading to artifacts. It also remains a great challenge to establish tip-enhanced fluorescence because of the quenching resulting from the proximity of the metal tip. Herein, we report shell-isolated tip-enhanced Raman and fluorescence spectroscopies by employing ultrathin shell-isolated tips fabricated by atomic layer deposition. Such shell-isolated tips not only show outstanding electromagnetic field enhancement in TERS but also exclude interference by contaminants, thus greatly promoting applications in solution. Tip-enhanced fluorescence has also been achieved using these shell-isolated tips, with enhancement factors of up to 1.7×103 , consistent with theoretical simulations. Furthermore, tip-enhanced Raman and fluorescence signals are acquired simultaneously, and their relative intensities can be manipulated by changing the shell thickness. This work opens a new avenue for ultrahigh resolution surface analysis using plasmon-enhanced spectroscopies.

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