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

Title: Surface-Enhanced Raman Scattering (SERS) Studies of Disc-on-Pillar (DOP) Arrays: Contrasting Enhancement Factor with Analytical Performance

Abstract

The use of nanomachining methods capable of reproducible construction of nano-arrayed devices have revolutionized the field of plasmonic sensing by the introduction of a diversity of rationally engineered designs. Significant strides have been made to fabricate plasmonic platforms with tailored interparticle gaps to improve their performance for surface-enhanced Raman scattering (SERS) applications. Over time, a dichotomy has emerged in the implementation of SERS for analytical applications, the construction of substrates, optimization of interparticle spacing as a means to optimize electromagnetic field enhancement at the localized surface plasmon level, and the substrate sensitivity over extended areas to achieve quantitative performance. Here, we assessed the enhancement factor of plasmonic Ag/SiO2/Si disc-on-pillar (DOP) arrays of variable pitch with its analytical performance for quantitative applications. Experimental data were compared with those from finite-difference time-domain (FDTD) simulations used in the optimization of the array dimensions. A self-assembled monolayer (SAM) of benzenethiol rendered highly reproducible signals (RSD ~4–10%) and SERS substrate enhancement factor (SSEF) values in the orders of 106–108 for all pitches. Furthermore, spectra corresponding to rhodamine 6G (R6G) and 4-aminobenzoic acid demonstrated the advantages of using the more densely packed DOP arrays with a 160 nm pitch (gap= 40 nm) for quantitation in spitemore » of the strongest SSEF was attained for a pitch of 520 nm corresponding to a 400 nm gap.« less

Authors:
ORCiD logo [1];  [2];  [2];  [3];  [1]
  1. Univ. of Puerto Rico, Mayaguez (Puerto Rico)
  2. Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)
  3. Univ. of Tennessee, Knoxville, TN (United States)
Publication Date:
Research Org.:
Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES)
OSTI Identifier:
1564208
Grant/Contract Number:  
AC05-00OR22725
Resource Type:
Accepted Manuscript
Journal Name:
Applied Spectroscopy
Additional Journal Information:
Journal Volume: 73; Journal Issue: 6; Journal ID: ISSN 0003-7028
Publisher:
Society for Applied Spectroscopy
Country of Publication:
United States
Language:
English
Subject:
36 MATERIALS SCIENCE; Surface-enhanced Raman spectroscopy; SERS; nanofabrication; finite-difference time-domain; FDTD; calibration sensitivity; SERS substrate enhancement factor; disc-on-pillar

Citation Formats

Velez, Raymond A., Lavrik, Nickolay V., Kravchenko, Ivan I., Sepaniak, Michael J., and Jesus, Marco A. De. Surface-Enhanced Raman Scattering (SERS) Studies of Disc-on-Pillar (DOP) Arrays: Contrasting Enhancement Factor with Analytical Performance. United States: N. p., 2019. Web. doi:10.1177/0003702819846503.
Velez, Raymond A., Lavrik, Nickolay V., Kravchenko, Ivan I., Sepaniak, Michael J., & Jesus, Marco A. De. Surface-Enhanced Raman Scattering (SERS) Studies of Disc-on-Pillar (DOP) Arrays: Contrasting Enhancement Factor with Analytical Performance. United States. doi:10.1177/0003702819846503.
Velez, Raymond A., Lavrik, Nickolay V., Kravchenko, Ivan I., Sepaniak, Michael J., and Jesus, Marco A. De. Mon . "Surface-Enhanced Raman Scattering (SERS) Studies of Disc-on-Pillar (DOP) Arrays: Contrasting Enhancement Factor with Analytical Performance". United States. doi:10.1177/0003702819846503. https://www.osti.gov/servlets/purl/1564208.
@article{osti_1564208,
title = {Surface-Enhanced Raman Scattering (SERS) Studies of Disc-on-Pillar (DOP) Arrays: Contrasting Enhancement Factor with Analytical Performance},
author = {Velez, Raymond A. and Lavrik, Nickolay V. and Kravchenko, Ivan I. and Sepaniak, Michael J. and Jesus, Marco A. De},
abstractNote = {The use of nanomachining methods capable of reproducible construction of nano-arrayed devices have revolutionized the field of plasmonic sensing by the introduction of a diversity of rationally engineered designs. Significant strides have been made to fabricate plasmonic platforms with tailored interparticle gaps to improve their performance for surface-enhanced Raman scattering (SERS) applications. Over time, a dichotomy has emerged in the implementation of SERS for analytical applications, the construction of substrates, optimization of interparticle spacing as a means to optimize electromagnetic field enhancement at the localized surface plasmon level, and the substrate sensitivity over extended areas to achieve quantitative performance. Here, we assessed the enhancement factor of plasmonic Ag/SiO2/Si disc-on-pillar (DOP) arrays of variable pitch with its analytical performance for quantitative applications. Experimental data were compared with those from finite-difference time-domain (FDTD) simulations used in the optimization of the array dimensions. A self-assembled monolayer (SAM) of benzenethiol rendered highly reproducible signals (RSD ~4–10%) and SERS substrate enhancement factor (SSEF) values in the orders of 106–108 for all pitches. Furthermore, spectra corresponding to rhodamine 6G (R6G) and 4-aminobenzoic acid demonstrated the advantages of using the more densely packed DOP arrays with a 160 nm pitch (gap= 40 nm) for quantitation in spite of the strongest SSEF was attained for a pitch of 520 nm corresponding to a 400 nm gap.},
doi = {10.1177/0003702819846503},
journal = {Applied Spectroscopy},
number = 6,
volume = 73,
place = {United States},
year = {2019},
month = {5}
}

Journal Article:
Free Publicly Available Full Text
Publisher's Version of Record

Save / Share:

Works referenced in this record:

Surface raman spectroelectrochemistry: Part I. Heterocyclic, aromatic, and aliphatic amines adsorbed on the anodized silver electrode
journal, November 1977

  • Jeanmaire, David L.; Van Duyne, Richard P.
  • Journal of Electroanalytical Chemistry and Interfacial Electrochemistry, Vol. 84, Issue 1, p. 1-20
  • DOI: 10.1016/S0022-0728(77)80224-6

Plasmonic Nanoparticles and Nanowires: Design, Fabrication and Application in Sensing
journal, March 2010

  • Vo-Dinh, Tuan; Dhawan, Anuj; Norton, Stephen J.
  • The Journal of Physical Chemistry C, Vol. 114, Issue 16
  • DOI: 10.1021/jp911355q

HREELS, XPS, and Electrochemical Study of Benzenethiol Adsorption on Au(111)
journal, January 1999

  • Whelan, Caroline M.; Smyth, Malcolm R.; Barnes, Colin J.
  • Langmuir, Vol. 15, Issue 1
  • DOI: 10.1021/la9806202

Efficient disc on pillar substrates for surface enhanced Raman spectroscopy
journal, January 2011

  • Wells, Sabrina M.; Polemi, Alessia; Lavrik, Nickolay V.
  • Chemical Communications, Vol. 47, Issue 13
  • DOI: 10.1039/c0cc05577h

Stamping plasmonic nanoarrays on SERS-supporting platforms
journal, April 2011

  • Bhandari, Deepak; Wells, Sabrina M.; Polemi, Alessia
  • Journal of Raman Spectroscopy, Vol. 42, Issue 11
  • DOI: 10.1002/jrs.2940

A Look at the Origin and Magnitude of the Chemical Contribution to the Enhancement Mechanism of Surface-Enhanced Raman Spectroscopy (SERS): Theory and Experiment
journal, July 2013

  • Valley, Nicholas; Greeneltch, Nathan; Van Duyne, Richard P.
  • The Journal of Physical Chemistry Letters, Vol. 4, Issue 16
  • DOI: 10.1021/jz4012383

Spectral Characteristics of Chemical Enhancement on SERS of Benzene-like Derivatives: Franck–Condon and Herzberg–Teller Contributions
journal, November 2015

  • Liu, Liqian; Chen, Danping; Ma, Huili
  • The Journal of Physical Chemistry C, Vol. 119, Issue 49
  • DOI: 10.1021/acs.jpcc.5b05910

Raman spectra of pyridine adsorbed at a silver electrode
journal, May 1974


Development of optimized nanogap plasmonic substrate for improved SERS enhancement
journal, May 2017

  • Perumal, Jayakumar; Gong, Tianxun; U. S., Dinish
  • AIP Advances, Vol. 7, Issue 5
  • DOI: 10.1063/1.4984769

Significance of chemical enhancement effects in surface-enhanced Raman scattering (SERS) signals of aniline and aminobiphenyl isomers
journal, November 2015


Understanding leaky modes: slab waveguide revisited
journal, January 2009

  • Hu, Jonathan; Menyuk, Curtis R.
  • Advances in Optics and Photonics, Vol. 1, Issue 1
  • DOI: 10.1364/AOP.1.000058

Dispersion Characteristics in Disk-on-Pillar Array Nanostructures for Surface-Enhanced Raman Spectroscopy
journal, June 2011

  • Polemi, Alessia; Wells, Sabrina M.; Lavrik, Nickolay V.
  • The Journal of Physical Chemistry C, Vol. 115, Issue 28
  • DOI: 10.1021/jp2032059

DFT Vibrational Calculations of Rhodamine 6G Adsorbed on Silver:  Analysis of Tip-Enhanced Raman Spectroscopy
journal, March 2005

  • Watanabe, Hiroyuki; Hayazawa, Norihiko; Inouye, Yasushi
  • The Journal of Physical Chemistry B, Vol. 109, Issue 11
  • DOI: 10.1021/jp045771u

Mosaic-like Silver Nanobowl Plasmonic Crystals as Highly Active Surface-Enhanced Raman Scattering Substrates
journal, July 2015

  • Baca, Alfred J.; Baca, Joshua; Montgomery, Jason M.
  • The Journal of Physical Chemistry C, Vol. 119, Issue 31
  • DOI: 10.1021/acs.jpcc.5b03824

SERS-based ultrasensitive sensing platform: An insight into design and practical applications
journal, April 2017

  • Yuan, Yufeng; Panwar, Nishtha; Yap, Stephanie Hui Kit
  • Coordination Chemistry Reviews, Vol. 337
  • DOI: 10.1016/j.ccr.2017.02.006

Silver Nanourchins in Plasmonics: Theoretical Investigation on the Optical Properties of the Branches
journal, May 2011

  • D’Agostino, Stefania; Della Sala, Fabio
  • The Journal of Physical Chemistry C, Vol. 115, Issue 24
  • DOI: 10.1021/jp202229y

Interaction of Plasmon and Molecular Resonances for Rhodamine 6G Adsorbed on Silver Nanoparticles
journal, June 2007

  • Zhao, Jing; Jensen, Lasse; Sung, Jiha
  • Journal of the American Chemical Society, Vol. 129, Issue 24
  • DOI: 10.1021/ja0707106

Surface‐enhanced Raman spectroscopy of benzene and benzene‐ d 6 adsorbed on silver
journal, December 1980

  • Moskovits, M.; DiLella, D. P.
  • The Journal of Chemical Physics, Vol. 73, Issue 12
  • DOI: 10.1063/1.440142

Persistent misconceptions regarding SERS
journal, January 2013

  • Moskovits, Martin
  • Physical Chemistry Chemical Physics, Vol. 15, Issue 15
  • DOI: 10.1039/c2cp44030j

Leaky Mode Resonance of Polyimide Waveguide Couples Metal Plasmon Resonance for Surface-Enhanced Raman Scattering
journal, October 2015

  • Wang, Shuai; Wu, Zhiyong; Chen, Lei
  • The Journal of Physical Chemistry C, Vol. 119, Issue 44
  • DOI: 10.1021/acs.jpcc.5b04791

Design and Characterization of Hybrid Morphology Nanoarrays as Plasmonic Raman Probes for Antimicrobial Detection
journal, November 2013

  • Olavarría-Fullerton, Jenifier; Velez, Raymond A.; Wells, Sabrina
  • Applied Spectroscopy, Vol. 67, Issue 11
  • DOI: 10.1366/13-07001

Plasmon-Sampled Surface-Enhanced Raman Excitation Spectroscopy
journal, July 2003

  • Haynes, Christy L.; Van Duyne, Richard P.
  • The Journal of Physical Chemistry B, Vol. 107, Issue 30
  • DOI: 10.1021/jp027749b

Nanofabrication of Densely Packed Metal—Polymer Arrays for Surface-Enhanced Raman Spectrometry
journal, December 2005


Enhanced raman spectra of ethylene and propylene adsorbed on silver
journal, August 1980


All-Dielectric Frequency Selective Surfaces with few Number of Periods
journal, January 2012

  • Barton, Jay H.; Rumpf, Raymond C.; Smith, Randall W.
  • Progress In Electromagnetics Research B, Vol. 41
  • DOI: 10.2528/PIERB12042404

High-density metallic nanogaps fabricated on solid substrates used for surface enhanced Raman scattering
journal, January 2012


Development of silver nanorod array based fiber optic probes for SERS detection
journal, September 2011

  • Zhu, Yu; Dluhy, Richard A.; Zhao, Yiping
  • Sensors and Actuators B: Chemical, Vol. 157, Issue 1, p. 42-50
  • DOI: 10.1016/j.snb.2011.03.024

Development of highly reproducible nanogap SERS substrates: Comparative performance analysis and its application for glucose sensing
journal, January 2011


Surface- and Resonance-Enhanced Micro-Raman Spectroscopy of Xanthene Dyes: From the Ensemble to Single Molecules
journal, January 2005


Surface Enhanced Raman Scattering Enhancement Factors:  A Comprehensive Study
journal, August 2007

  • Le Ru, E. C.; Blackie, E.; Meyer, M.
  • The Journal of Physical Chemistry C, Vol. 111, Issue 37
  • DOI: 10.1021/jp0687908

Molecular Orientation and Ordered Structure of Benzenethiol Adsorbed on Gold(111)
journal, April 2000

  • Wan, Li-Jun; Terashima, Mimi; Noda, Hiroyuki
  • The Journal of Physical Chemistry B, Vol. 104, Issue 15
  • DOI: 10.1021/jp993328r

Fractal Nanoparticle Plasmonics: The Cayley Tree
journal, February 2015


Chemical Contribution to SERS Enhancement: An Experimental Study on a Series of Polymethine Dyes on Silver Nanoaggregates
journal, June 2016


Plasmonic Nanogap-Enhanced Raman Scattering with Nanoparticles
journal, November 2016


Fluorescence efficiency of laser dyes
journal, May 1976

  • Drexhage, K. H.
  • Journal of Research of the National Bureau of Standards Section A: Physics and Chemistry, Vol. 80A, Issue 3
  • DOI: 10.6028/jres.080A.044

Ab initio study of optical properties of rhodamine 6G molecular dimers
journal, January 2006

  • Gavrilenko, V. I.; Noginov, M. A.
  • The Journal of Chemical Physics, Vol. 124, Issue 4
  • DOI: 10.1063/1.2158987

Waveguide-Enhanced Surface Plasmons for Ultrasensitive SERS Detection
journal, September 2013

  • Gu, Yuejiao; Xu, Shuping; Li, Haibo
  • The Journal of Physical Chemistry Letters, Vol. 4, Issue 18
  • DOI: 10.1021/jz401512k

Phonon-enhanced light–matter interaction at the nanometre scale
journal, July 2002

  • Hillenbrand, R.; Taubner, T.; Keilmann, F.
  • Nature, Vol. 418, Issue 6894
  • DOI: 10.1038/nature00899

Modulation of hot regions in waveguide-based evanescent-field-coupled localized surface plasmons for plasmon-enhanced spectroscopy
journal, January 2017

  • Wang, Hailong; Wang, Yuyang; Wang, Yi
  • Photonics Research, Vol. 5, Issue 5
  • DOI: 10.1364/PRJ.5.000527

    Works referencing / citing this record:

    SERS-based ultrasensitive sensing platform: An insight into design and practical applications
    journal, April 2017

    • Yuan, Yufeng; Panwar, Nishtha; Yap, Stephanie Hui Kit
    • Coordination Chemistry Reviews, Vol. 337
    • DOI: 10.1016/j.ccr.2017.02.006

    Development of silver nanorod array based fiber optic probes for SERS detection
    journal, September 2011

    • Zhu, Yu; Dluhy, Richard A.; Zhao, Yiping
    • Sensors and Actuators B: Chemical, Vol. 157, Issue 1, p. 42-50
    • DOI: 10.1016/j.snb.2011.03.024

    Design and Characterization of Hybrid Morphology Nanoarrays as Plasmonic Raman Probes for Antimicrobial Detection
    journal, November 2013

    • Olavarría-Fullerton, Jenifier; Velez, Raymond A.; Wells, Sabrina
    • Applied Spectroscopy, Vol. 67, Issue 11
    • DOI: 10.1366/13-07001

    Surface Enhanced Raman Scattering Enhancement Factors:  A Comprehensive Study
    journal, August 2007

    • Le Ru, E. C.; Blackie, E.; Meyer, M.
    • The Journal of Physical Chemistry C, Vol. 111, Issue 37
    • DOI: 10.1021/jp0687908

    Fractal Nanoparticle Plasmonics: The Cayley Tree
    journal, February 2015


    Dispersion Characteristics in Disk-on-Pillar Array Nanostructures for Surface-Enhanced Raman Spectroscopy
    journal, June 2011

    • Polemi, Alessia; Wells, Sabrina M.; Lavrik, Nickolay V.
    • The Journal of Physical Chemistry C, Vol. 115, Issue 28
    • DOI: 10.1021/jp2032059

    Interaction of Plasmon and Molecular Resonances for Rhodamine 6G Adsorbed on Silver Nanoparticles
    journal, June 2007

    • Zhao, Jing; Jensen, Lasse; Sung, Jiha
    • Journal of the American Chemical Society, Vol. 129, Issue 24
    • DOI: 10.1021/ja0707106

    Development of highly reproducible nanogap SERS substrates: Comparative performance analysis and its application for glucose sensing
    journal, January 2011


    Surface‐enhanced Raman spectroscopy of benzene and benzene‐ d 6 adsorbed on silver
    journal, December 1980

    • Moskovits, M.; DiLella, D. P.
    • The Journal of Chemical Physics, Vol. 73, Issue 12
    • DOI: 10.1063/1.440142

    Surface- and Resonance-Enhanced Micro-Raman Spectroscopy of Xanthene Dyes: From the Ensemble to Single Molecules
    journal, January 2005


    Phonon-enhanced light–matter interaction at the nanometre scale
    journal, July 2002

    • Hillenbrand, R.; Taubner, T.; Keilmann, F.
    • Nature, Vol. 418, Issue 6894
    • DOI: 10.1038/nature00899

    Stamping plasmonic nanoarrays on SERS-supporting platforms
    journal, April 2011

    • Bhandari, Deepak; Wells, Sabrina M.; Polemi, Alessia
    • Journal of Raman Spectroscopy, Vol. 42, Issue 11
    • DOI: 10.1002/jrs.2940

    Waveguide-Enhanced Surface Plasmons for Ultrasensitive SERS Detection
    journal, September 2013

    • Gu, Yuejiao; Xu, Shuping; Li, Haibo
    • The Journal of Physical Chemistry Letters, Vol. 4, Issue 18
    • DOI: 10.1021/jz401512k

    Nanofabrication of Densely Packed Metal—Polymer Arrays for Surface-Enhanced Raman Spectrometry
    journal, December 2005


    Raman spectra of pyridine adsorbed at a silver electrode
    journal, May 1974


    Molecular Orientation and Ordered Structure of Benzenethiol Adsorbed on Gold(111)
    journal, April 2000

    • Wan, Li-Jun; Terashima, Mimi; Noda, Hiroyuki
    • The Journal of Physical Chemistry B, Vol. 104, Issue 15
    • DOI: 10.1021/jp993328r

    Ab initio study of optical properties of rhodamine 6G molecular dimers
    journal, January 2006

    • Gavrilenko, V. I.; Noginov, M. A.
    • The Journal of Chemical Physics, Vol. 124, Issue 4
    • DOI: 10.1063/1.2158987

    Plasmonic Nanogap-Enhanced Raman Scattering with Nanoparticles
    journal, November 2016


    Enhanced raman spectra of ethylene and propylene adsorbed on silver
    journal, August 1980


    Significance of chemical enhancement effects in surface-enhanced Raman scattering (SERS) signals of aniline and aminobiphenyl isomers
    journal, November 2015


    Development of optimized nanogap plasmonic substrate for improved SERS enhancement
    journal, May 2017

    • Perumal, Jayakumar; Gong, Tianxun; U. S., Dinish
    • AIP Advances, Vol. 7, Issue 5
    • DOI: 10.1063/1.4984769

    DFT Vibrational Calculations of Rhodamine 6G Adsorbed on Silver:  Analysis of Tip-Enhanced Raman Spectroscopy
    journal, March 2005

    • Watanabe, Hiroyuki; Hayazawa, Norihiko; Inouye, Yasushi
    • The Journal of Physical Chemistry B, Vol. 109, Issue 11
    • DOI: 10.1021/jp045771u

    A Look at the Origin and Magnitude of the Chemical Contribution to the Enhancement Mechanism of Surface-Enhanced Raman Spectroscopy (SERS): Theory and Experiment
    journal, July 2013

    • Valley, Nicholas; Greeneltch, Nathan; Van Duyne, Richard P.
    • The Journal of Physical Chemistry Letters, Vol. 4, Issue 16
    • DOI: 10.1021/jz4012383

    Efficient disc on pillar substrates for surface enhanced Raman spectroscopy
    journal, January 2011

    • Wells, Sabrina M.; Polemi, Alessia; Lavrik, Nickolay V.
    • Chemical Communications, Vol. 47, Issue 13
    • DOI: 10.1039/c0cc05577h

    Spectral Characteristics of Chemical Enhancement on SERS of Benzene-like Derivatives: Franck–Condon and Herzberg–Teller Contributions
    journal, November 2015

    • Liu, Liqian; Chen, Danping; Ma, Huili
    • The Journal of Physical Chemistry C, Vol. 119, Issue 49
    • DOI: 10.1021/acs.jpcc.5b05910

    Chemical Contribution to SERS Enhancement: An Experimental Study on a Series of Polymethine Dyes on Silver Nanoaggregates
    journal, June 2016


    HREELS, XPS, and Electrochemical Study of Benzenethiol Adsorption on Au(111)
    journal, January 1999

    • Whelan, Caroline M.; Smyth, Malcolm R.; Barnes, Colin J.
    • Langmuir, Vol. 15, Issue 1
    • DOI: 10.1021/la9806202

    Leaky Mode Resonance of Polyimide Waveguide Couples Metal Plasmon Resonance for Surface-Enhanced Raman Scattering
    journal, October 2015

    • Wang, Shuai; Wu, Zhiyong; Chen, Lei
    • The Journal of Physical Chemistry C, Vol. 119, Issue 44
    • DOI: 10.1021/acs.jpcc.5b04791

    Persistent misconceptions regarding SERS
    journal, January 2013

    • Moskovits, Martin
    • Physical Chemistry Chemical Physics, Vol. 15, Issue 15
    • DOI: 10.1039/c2cp44030j

    Plasmon-Sampled Surface-Enhanced Raman Excitation Spectroscopy
    journal, July 2003

    • Haynes, Christy L.; Van Duyne, Richard P.
    • The Journal of Physical Chemistry B, Vol. 107, Issue 30
    • DOI: 10.1021/jp027749b

    Plasmonic Nanoparticles and Nanowires: Design, Fabrication and Application in Sensing
    journal, March 2010

    • Vo-Dinh, Tuan; Dhawan, Anuj; Norton, Stephen J.
    • The Journal of Physical Chemistry C, Vol. 114, Issue 16
    • DOI: 10.1021/jp911355q

    Silver Nanourchins in Plasmonics: Theoretical Investigation on the Optical Properties of the Branches
    journal, May 2011

    • D’Agostino, Stefania; Della Sala, Fabio
    • The Journal of Physical Chemistry C, Vol. 115, Issue 24
    • DOI: 10.1021/jp202229y

    Mosaic-like Silver Nanobowl Plasmonic Crystals as Highly Active Surface-Enhanced Raman Scattering Substrates
    journal, July 2015

    • Baca, Alfred J.; Baca, Joshua; Montgomery, Jason M.
    • The Journal of Physical Chemistry C, Vol. 119, Issue 31
    • DOI: 10.1021/acs.jpcc.5b03824