skip to main content
OSTI.GOV title logo U.S. Department of Energy
Office of Scientific and Technical Information

Title: Combined measurement of directional Raman scattering and surface-plasmon-polariton cone from adsorbates on smooth planar gold surfaces

Abstract

Directional-surface-plasmon-coupled Raman scattering (directional RS) has the combined benefits of surface plasmon resonance and Raman spectroscopy, and provides the ability to measure adsorption and monolayer-sensitive chemical information. Directional RS is performed by optically coupling a 50-nm gold film to a Weierstrass prism in the Kretschmann configuration and scanning the angle of the incident laser under total internal reflection. The collected parameters on the prism side of the interface include a full surface-plasmon-polariton cone and the full Raman signal radiating from the cone as a function of incident angle. An instrument for performing directional RS and a quantitative study of the instrumental parameters are herein reported. To test the sensitivity and quantify the instrument parameters, self-assembled monolayers and 10 to 100-nm polymer films are studied. The signals are found to be well-modeled by two calculated angle-dependent parameters: three-dimensional finite-difference time-domain calculations of the electric field generated in the sample layer and projected to the far-field, and Fresnel calculations of the reflected light intensity. This is the first report of the quantitative study of the full surface-plasmon-polariton cone intensity, cone diameter, and directional Raman signal as a function of incident angle. We propose that directional RS is a viable alternative to surfacemore » plasmon resonance when added chemical information is beneficial.« less

Authors:
ORCiD logo [1]; ORCiD logo [2]; ORCiD logo [3]; ORCiD logo [1]
  1. Ames Lab. and Iowa State Univ., Ames, IA (United States). Dept. of Chemistry
  2. Surface Photonics Inc., Madison, WI (United States)
  3. The Ames Laboratory; U.S. Department of Energy; Ames; USA; Department of Chemistry
Publication Date:
Research Org.:
Ames Laboratory (AMES), Ames, IA (United States)
Sponsoring Org.:
USDOE
OSTI Identifier:
1406906
Report Number(s):
IS-J-9409
Journal ID: ISSN 0003-2654; ANALAO
Grant/Contract Number:
AC02-07CH11358
Resource Type:
Journal Article: Accepted Manuscript
Journal Name:
Analyst
Additional Journal Information:
Journal Name: Analyst; Journal ID: ISSN 0003-2654
Publisher:
Royal Society of Chemistry
Country of Publication:
United States
Language:
English
Subject:
47 OTHER INSTRUMENTATION

Citation Formats

Nyamekye, Charles K. A., Weibel, Stephen C., Bobbitt, Jonathan M., and Smith, Emily A. Combined measurement of directional Raman scattering and surface-plasmon-polariton cone from adsorbates on smooth planar gold surfaces. United States: N. p., 2017. Web. doi:10.1039/C7AN01299C.
Nyamekye, Charles K. A., Weibel, Stephen C., Bobbitt, Jonathan M., & Smith, Emily A. Combined measurement of directional Raman scattering and surface-plasmon-polariton cone from adsorbates on smooth planar gold surfaces. United States. doi:10.1039/C7AN01299C.
Nyamekye, Charles K. A., Weibel, Stephen C., Bobbitt, Jonathan M., and Smith, Emily A. Fri . "Combined measurement of directional Raman scattering and surface-plasmon-polariton cone from adsorbates on smooth planar gold surfaces". United States. doi:10.1039/C7AN01299C.
@article{osti_1406906,
title = {Combined measurement of directional Raman scattering and surface-plasmon-polariton cone from adsorbates on smooth planar gold surfaces},
author = {Nyamekye, Charles K. A. and Weibel, Stephen C. and Bobbitt, Jonathan M. and Smith, Emily A.},
abstractNote = {Directional-surface-plasmon-coupled Raman scattering (directional RS) has the combined benefits of surface plasmon resonance and Raman spectroscopy, and provides the ability to measure adsorption and monolayer-sensitive chemical information. Directional RS is performed by optically coupling a 50-nm gold film to a Weierstrass prism in the Kretschmann configuration and scanning the angle of the incident laser under total internal reflection. The collected parameters on the prism side of the interface include a full surface-plasmon-polariton cone and the full Raman signal radiating from the cone as a function of incident angle. An instrument for performing directional RS and a quantitative study of the instrumental parameters are herein reported. To test the sensitivity and quantify the instrument parameters, self-assembled monolayers and 10 to 100-nm polymer films are studied. The signals are found to be well-modeled by two calculated angle-dependent parameters: three-dimensional finite-difference time-domain calculations of the electric field generated in the sample layer and projected to the far-field, and Fresnel calculations of the reflected light intensity. This is the first report of the quantitative study of the full surface-plasmon-polariton cone intensity, cone diameter, and directional Raman signal as a function of incident angle. We propose that directional RS is a viable alternative to surface plasmon resonance when added chemical information is beneficial.},
doi = {10.1039/C7AN01299C},
journal = {Analyst},
number = ,
volume = ,
place = {United States},
year = {Fri Sep 15 00:00:00 EDT 2017},
month = {Fri Sep 15 00:00:00 EDT 2017}
}

Journal Article:
Free Publicly Available Full Text
This content will become publicly available on September 15, 2018
Publisher's Version of Record

Save / Share:
  • We describe the theory, design, and performance of a new surface-plasmon-polariton-(SPP) assisted Raman scattering instrument that exploits the Kretschmann geometry. In contrast to previous methods, our device allows the entire SPP emission cone to be collected, thus optimizing the detected Raman intensity. This advantage makes surface Raman scattering from adsorbates on relatively smooth or single-crystal silver films possible with routine optics and electronics in the rest of the system. We demonstrate the concept with data acquired from a monolayer of paranitrosodimethylanaline (pNDMA) on nearly smooth polycrystalline Ag and single-crystal Ag(111) with air or liquid as the ambient medium.
  • This paper presents a theoretical and preliminary experimental evaluation of a Kretschmann prism coupler method used in Raman scattering experiments with molecular adsorbates. The theoretical enhancement of Raman scattering intensity, which can be as high as a factor of 1000, is calculated by using an exact method of 2 X 2 transfer matrices. Preliminary experiments, designed to investigate the feasibility of this technique under ultra-high-vacuum conditions, show that monolayer sensitivity can be practically achieved. The authors discuss the optimum experimental configuration, as well as the factors that can seriously limit achievable enhancement levels.
  • The structures and coalescence behavior of size-selected, matrix-isolated silicon clusters have been studied using surface-plasmon-polariton (SPP) enhanced Raman spectroscopy. The cluster ions were produced in a laser vaporization source, mass selected then deposited into a co-condensed matrix of Ar, Kr or N{sub 2} on a liquid He cooled substrate. Raman spectra from monodisperse samples of the smaller clusters studied, Si{sub 4}, Si{sub 6} and Si{sub 7}, show sharp, well-resolved, vibrations which are in good agreement with predictions based on {ital ab initio} calculations. From these comparisons we confirm that Si{sub 4} is a planar rhombus, and assign Si{sub 6} asmore » a distorted octahedron and Si{sub 7} as a pentagonal bypyramid. Si{sub 5} depositions down to 5 eV did not reveal a measurable Raman spectrum under our experimental conditions. Evidence for cluster{endash}cluster aggregation (or fragmentation) was observed under some conditions, even for a {open_quotes}magic number{close_quotes} cluster such as Si{sub 6}. The spectra of the aggregated small clusters were identical to those observed for directly deposited larger cluster {open_quotes}bands,{close_quotes} such as Si{sub 25{endash}35}. The Raman spectra of the aggregated clusters bear some similarity to those of bulk amorphous silicon. Cluster-deposited thin films were prepared by sublimating the matrix material. Even under these {open_quotes}soft landing{close_quotes} conditions, changes in the Raman spectrum are observed with the thin films showing even greater similarity to amorphous silicon. {copyright} {ital 1999 American Institute of Physics.}« less
  • The paper represents a novel approach to investigating localized surface plasmon (LSP) resonance modes of nanoporous Au nanorods (NRs) in a solution phase with control over surface morphology. Au NRs, which have distinctive features such as nanopores and ligaments, showed interesting LSP resonance modes depending on the surface morphology and the total length of the structure. Compared with the analogous smooth surface NRs, the LSP modes of nanoporous NRs are red-shifted, which can be interpreted as a longer effective rod length and larger amplitude of plasmon oscillation.
  • We introduce the quantum mechanical formalism for treating surface plasmon polariton scattering at an interface. Our developed theory--which differs fundamentally from the analogous photonic scenario--is used to investigate the possibility of plasmonic beam splitters at the quantum level. Remarkably, we find that a wide range of splitting ratios can be reached. As an application, we characterize a 50:50 plasmonic beam splitter and investigate first-order quantum interference of surface plasmon polaritons. The results of this theoretical study show that surface plasmon beam splitters are able to reliably and efficiently operate in the quantum domain.