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Title:Voltage-dependent FTIR and 2D infrared spectroscopies within the electric double layer using a plasmonic and conductive electrode
Authors:ID Yang, Nan (Author)
ID Ryan, Matthew J. (Author)
ID Son, Minjung (Author)
ID Mavrič, Andraž (Author)
ID Zanni, Martin (Author)
Files:.pdf acs.jpcb.2c08431.pdf (6,07 MB)
MD5: 93BC186C756081A0B94A3E612AC7F6A8
Work type:Unknown
Typology:1.01 - Original Scientific Article
Organization:UNG - University of Nova Gorica
Abstract:Strong electric fields exist between the electric double layer and charged surfaces. These fields impact molecular structures and chemistry at interfaces. We have developed a transparent electrode with infrared plasmonic enhancement sufficient to measure FTIR and two-dimensional infrared spectra at submonolayer coverages on the surface to which a voltage can be applied. Our device consists of an infrared transparent substrate, a 10–20 nm layer of conductive indium tin oxide (ITO), an electrically resistive layer of 3–5 nm Al2O3, and a 3 nm layer of nonconductive plasmonic gold. The materials and thicknesses are set to maximize the surface number density of the monolayer molecules, electrical conductivity, and plasmonic enhancement while minimizing background signals and avoiding Fano line shape distortions. The design was optimized by iteratively characterizing the material roughness and thickness with atomic force microscopy and electron microscopy and by monitoring the plasmon resonance enhancement with spectroscopy. The design is robust to repeated fabrication. This new electrode is tested on nitrile functional groups using a monolayer of 4-mercaptobenzonitrile as well as on CO and CC stretching modes using 4-mercaptobenzoic acid methyl ester. A voltage-dependent Stark shift is observed on both monolayers. We also observe that the transition dipole strength of the CN mode scales linearly with the applied voltage, providing a second way of measuring the surface electric field strength. We anticipate that this cell will enable many new voltage-dependent infrared experiments under applied voltages.
Keywords:two-dimensional infrared spectroscopy, infrared transparent substrate, voltage-dependent infrared experiments
Publication status:Published
Publication version:Author Accepted Manuscript
Publication date:01.01.2023
Year of publishing:2023
Number of pages:str. 2083–2091
Numbering:Vol. 127, issue 9
PID:20.500.12556/RUNG-7999-bf4acfb9-6dd2-e39f-5a2b-fcd108fadd39 New window
COBISS.SI-ID:142947331 New window
ISSN on article:1520-6106
DOI:10.1021/acs.jpcb.2c08431 New window
Publication date in RUNG:24.02.2023
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Record is a part of a journal

Title:The journal of physical chemistry. Condensed matter, materials, surfaces, interfaces & biophysical
Shortened title:J. phys. chem., B Condens. mater. surf. interfaces biophys.
Publisher:American Chemical Society
COBISS.SI-ID:14241063 New window

Document is financed by a project

Funder:ARRS - Slovenian Research Agency
Project number:J2-2498
Name:Redukcija ogljikovega dioksida na katalizatorju z izoliranimi atomi za tvorbo spojin z dodano vrednostjo

Funder:ARIS - Slovenian Research and Innovation Agency
Project number:P2-0412
Name:Heterogeni procesi na površinah trdnin za trajnostne tehnologije


License:CC BY-NC-ND 4.0, Creative Commons Attribution-NonCommercial-NoDerivatives 4.0 International
Description:The most restrictive Creative Commons license. This only allows people to download and share the work for no commercial gain and for no other purposes.
Licensing start date:24.02.2023

Secondary language

Keywords:two-dimensional infrared spectroscopy, infrared transparent substrate, voltage-dependent infrared experiments