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Title: Direct Experimental Evidence of Hot Carrier-Driven Chemical Processes in Tip-Enhanced Raman Spectroscopy (TERS)

Abstract

Nanoscale localization of electromagnetic fields using metallic nanostructures can catalyze chemical reactions in their immediate vicinity. Local optical field confinement and enhancement is also exploited to attain single molecule detection sensitivity in surface and tip-enhanced Raman (TER) spectroscopy. In this work reported herein, we observe and investigate the sporadic formation of 4-nitrobenzenethiolate upon TER imaging of a 4-nitrobenzenethiol (4NBT) monolayer on Au(111). Density functional theory (DFT), finite-difference time-domain (FDTD), and finite element method (FEM) calculations together confirm that this chemical reaction does not occur as a result of thermal desorption of the molecule, which requires temperatures in excess of 2100 K at the tip-sample junction. Our combined experimental and theoretical analyses strongly suggest that the chemical transformations observed throughout the course of TERS mapping is not driven by plasmonic photothermal heating, but rather by plasmon-induced hot carriers.

Authors:
ORCiD logo [1];  [2];  [3]; ORCiD logo [3]; ORCiD logo [4]; ORCiD logo [2]; ORCiD logo [1]
  1. Texas A & M Univ., College Station, TX (United States)
  2. Illinois Inst. of Technology, Chicago, IL (United States)
  3. Univ. of Texas at San Antonio, TX (United States)
  4. Pacific Northwest National Lab. (PNNL), Richland, WA (United States)
Publication Date:
Research Org.:
Pacific Northwest National Lab. (PNNL), Richland, WA (United States)
Sponsoring Org.:
Governor’s University Research Initiative (GURI); US Army Research Office (ARO); USDOE Office of Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences, and Biosciences Division
OSTI Identifier:
1599167
Report Number(s):
PNNL-SA-149743
Journal ID: ISSN 1932-7447
Grant/Contract Number:  
AC05-76RL01830; 12-2016, M1700437; W911NF-18-1-0439
Resource Type:
Accepted Manuscript
Journal Name:
Journal of Physical Chemistry. C
Additional Journal Information:
Journal Volume: 124; Journal Issue: 3; Journal ID: ISSN 1932-7447
Publisher:
American Chemical Society
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; Desorption; anions; metals; gold; raman spectroscopy

Citation Formats

Wang, Rui, Li, Jingbai, Rigor, Joel, Large, Nicolas, El-Khoury, Patrick Z., Rogachev, Andrey Yu., and Kurouski, Dmitry. Direct Experimental Evidence of Hot Carrier-Driven Chemical Processes in Tip-Enhanced Raman Spectroscopy (TERS). United States: N. p., 2019. Web. https://doi.org/10.1021/acs.jpcc.9b12002.
Wang, Rui, Li, Jingbai, Rigor, Joel, Large, Nicolas, El-Khoury, Patrick Z., Rogachev, Andrey Yu., & Kurouski, Dmitry. Direct Experimental Evidence of Hot Carrier-Driven Chemical Processes in Tip-Enhanced Raman Spectroscopy (TERS). United States. https://doi.org/10.1021/acs.jpcc.9b12002
Wang, Rui, Li, Jingbai, Rigor, Joel, Large, Nicolas, El-Khoury, Patrick Z., Rogachev, Andrey Yu., and Kurouski, Dmitry. Thu . "Direct Experimental Evidence of Hot Carrier-Driven Chemical Processes in Tip-Enhanced Raman Spectroscopy (TERS)". United States. https://doi.org/10.1021/acs.jpcc.9b12002. https://www.osti.gov/servlets/purl/1599167.
@article{osti_1599167,
title = {Direct Experimental Evidence of Hot Carrier-Driven Chemical Processes in Tip-Enhanced Raman Spectroscopy (TERS)},
author = {Wang, Rui and Li, Jingbai and Rigor, Joel and Large, Nicolas and El-Khoury, Patrick Z. and Rogachev, Andrey Yu. and Kurouski, Dmitry},
abstractNote = {Nanoscale localization of electromagnetic fields using metallic nanostructures can catalyze chemical reactions in their immediate vicinity. Local optical field confinement and enhancement is also exploited to attain single molecule detection sensitivity in surface and tip-enhanced Raman (TER) spectroscopy. In this work reported herein, we observe and investigate the sporadic formation of 4-nitrobenzenethiolate upon TER imaging of a 4-nitrobenzenethiol (4NBT) monolayer on Au(111). Density functional theory (DFT), finite-difference time-domain (FDTD), and finite element method (FEM) calculations together confirm that this chemical reaction does not occur as a result of thermal desorption of the molecule, which requires temperatures in excess of 2100 K at the tip-sample junction. Our combined experimental and theoretical analyses strongly suggest that the chemical transformations observed throughout the course of TERS mapping is not driven by plasmonic photothermal heating, but rather by plasmon-induced hot carriers.},
doi = {10.1021/acs.jpcc.9b12002},
journal = {Journal of Physical Chemistry. C},
number = 3,
volume = 124,
place = {United States},
year = {2019},
month = {12}
}

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