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

被引:49
作者
Wang, Rui [1 ]
Li, Jingbai [2 ]
Rigor, Joel [3 ]
Large, Nicolas [3 ]
El-Khoury, Patrick Z. [4 ]
Rogachev, Andrey Yu. [2 ]
Kurouski, Dmitry [1 ]
机构
[1] Texas A&M Univ, College Stn, TX 77843 USA
[2] IIT, Chicago, IL 60616 USA
[3] Univ Texas San Antonio, San Antonio, TX USA
[4] Pacific Northwest Natl Lab, Richland, WA 99352 USA
关键词
ELECTRIC-FIELDS; NEAR-FIELD; SURFACE; SCATTERING; MOLECULES; GOLD; SERS; NANOPARTICLES; DYNAMICS; CO;
D O I
10.1021/acs.jpcc.9b12002
中图分类号
O64 [物理化学(理论化学)、化学物理学];
学科分类号
070304 ; 081704 ;
摘要
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, 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.
引用
收藏
页码:2238 / 2244
页数:7
相关论文
共 53 条
  • [21] The impact of the resolution of the identity approximate integral method on modern ab initio algorithm development
    Kendall, RA
    Fruchtl, HA
    [J]. THEORETICAL CHEMISTRY ACCOUNTS, 1997, 97 (1-4) : 158 - 163
  • [22] How to deal with the loss in plasmonics and metamaterials
    Khurgin, Jacob B.
    [J]. NATURE NANOTECHNOLOGY, 2015, 10 (01) : 2 - 6
  • [23] Photooxidative Coupling of Thiophenol Derivatives to Disulfides
    Kim, Hyung Jun
    Yoon, Jun Hee
    Yoon, Sangwoon
    [J]. JOURNAL OF PHYSICAL CHEMISTRY A, 2010, 114 (45) : 12010 - 12015
  • [24] THEORY OF RAMAN-SCATTERING BY MOLECULES ADSORBED ON ELECTRODE SURFACES
    KING, FW
    VANDUYNE, RP
    SCHATZ, GC
    [J]. JOURNAL OF CHEMICAL PHYSICS, 1978, 69 (10) : 4472 - 4481
  • [25] Single molecule detection using surface-enhanced Raman scattering (SERS)
    Kneipp, K
    Wang, Y
    Kneipp, H
    Perelman, LT
    Itzkan, I
    Dasari, R
    Feld, MS
    [J]. PHYSICAL REVIEW LETTERS, 1997, 78 (09) : 1667 - 1670
  • [26] Unraveling near-field and far-field relationships for 3D SERS substrates - a combined experimental and theoretical analysis
    Kurouski, Dmitry
    Large, Nicolas
    Chiang, Naihao
    Greeneltch, Nathan
    Carron, Keith T.
    Seideman, Tamar
    Schatz, George C.
    Van Duyne, Richard P.
    [J]. ANALYST, 2016, 141 (05) : 1779 - 1788
  • [27] Structure and Composition of Insulin Fibril Surfaces Probed by TERS
    Kurouski, Dmitry
    Deckert-Gaudig, Tanja
    Deckert, Volker
    Lednev, Igor K.
    [J]. JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2012, 134 (32) : 13323 - 13329
  • [28] In situ surface-enhanced Raman spectroscopic monitoring electrochemical and surface plasmon resonance synergetic catalysis on dehydroxylation of PHTP at Ag electrodes
    Li, Xu
    Zhang, Chenjie
    Wu, Qian
    Zhang, Jing
    Xu, Minmin
    Yuan, Yaxian
    Yao, Jianlin
    [J]. JOURNAL OF RAMAN SPECTROSCOPY, 2018, 49 (12) : 1928 - 1937
  • [29] Direct Nanospectroscopic Verification of the Amyloid Aggregation Pathway
    Lipiec, Ewelina
    Perez-Guaita, David
    Kaderli, Janina
    Wood, Bayden R.
    Zenobi, Renato
    [J]. ANGEWANDTE CHEMIE-INTERNATIONAL EDITION, 2018, 57 (28) : 8519 - 8524
  • [30] Interplay between plasmon and single-particle excitations in a metal nanocluster
    Ma, Jie
    Wang, Zhi
    Wang, Lin-Wang
    [J]. NATURE COMMUNICATIONS, 2015, 6