Plasmon-enhanced coherent Raman scattering microscopy has reached single-molecule detection sensitivity. Due to the different driven fields, there are significant differences between a coherent Raman scattering process and its plasmon-enhanced derivative. The commonly accepted line shapes for coherent anti-Stokes Raman scattering and stimulated Raman scattering do not hold for the plasmon-enhanced condition. Here, we present a theoretical model that describes the spectral line shapes in plasmon-enhanced coherent anti-Stokes Raman scattering (PECARS). Experimentally, we measured PECARS and plasmon-enhanced stimulated Raman scattering (PESRS) spectra of 4-mercaptopyridine adsorbed on the self-assembled Au nanoparticle (NP) substrate and aggregated Au NP colloids. The PECARS spectra show a nondispersive line shape, while the PESRS spectra exhibit a dispersive line shape. PECARS shows a higher signal to noise ratio and a larger enhancement factor than PESRS from the same specimen. It is verified that the nonresonant background in PECARS originates from the photoluminescence of nanostructures. The decoupling of background and the vibrational resonance component results in the nondispersive line shape in PECARS. More local electric field enhancements are involved in the PECARS process than in PESRS, which results in a higher enhancement factor in PECARS. The current work provides new insight into the mechanism of plasmon-enhanced coherent Raman scattering and helps to optimize the experimental design for ultrasensitive chemical imaging.
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21 January 2021
Research Article|
January 15 2021
Plasmon-enhanced coherent anti-stokes Raman scattering vs plasmon-enhanced stimulated Raman scattering: Comparison of line shape and enhancement factor
Special Collection:
Spectroscopy and Microscopy of Plasmonic Systems
Cheng Zong;
Cheng Zong
1
Department of Electrical and Computer Engineering, Boston University
, Boston, Massachusetts 02215, USA
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Yurun Xie;
Yurun Xie
2
State Key Laboratory of Molecular Reaction Dynamics, Dalian Institute of Chemical Physics, Chinese Academy of Sciences
, Dalian 116023, China
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Meng Zhang;
Meng Zhang
1
Department of Electrical and Computer Engineering, Boston University
, Boston, Massachusetts 02215, USA
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Yimin Huang;
Yimin Huang
3
Department of Chemistry, Boston University
, Boston, Massachusetts 02215, USA
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Chen Yang
;
Chen Yang
1
Department of Electrical and Computer Engineering, Boston University
, Boston, Massachusetts 02215, USA
3
Department of Chemistry, Boston University
, Boston, Massachusetts 02215, USA
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Ji-Xin Cheng
Ji-Xin Cheng
a)
1
Department of Electrical and Computer Engineering, Boston University
, Boston, Massachusetts 02215, USA
3
Department of Chemistry, Boston University
, Boston, Massachusetts 02215, USA
4
Department of Biomedical Engineering, Photonics Center, Boston University
, Boston, Massachusetts 02215, USA
a)Author to whom correspondence should be addressed: jxcheng@bu.edu
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a)Author to whom correspondence should be addressed: jxcheng@bu.edu
Note: This paper is part of the JCP Special Topic on Spectroscopy and Microscopy of Plasmonic Systems.
J. Chem. Phys. 154, 034201 (2021)
Article history
Received:
October 26 2020
Accepted:
December 28 2020
Citation
Cheng Zong, Yurun Xie, Meng Zhang, Yimin Huang, Chen Yang, Ji-Xin Cheng; Plasmon-enhanced coherent anti-stokes Raman scattering vs plasmon-enhanced stimulated Raman scattering: Comparison of line shape and enhancement factor. J. Chem. Phys. 21 January 2021; 154 (3): 034201. https://doi.org/10.1063/5.0035163
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