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

Title: Self-Assembly of Large Gold Nanoparticles for Surface-Enhanced Raman Spectroscopy

Journal Article · · ACS Applied Materials and Interfaces

Performance of portable technologies from mobile phones to electric vehicles is currently limited by the energy density and lifetime of lithium batteries. Expanding the limits of battery technology requires in situ detection of trace components at electrode–electrolyte interphases. Surface-enhance Raman spectroscopy could satisfy this need if a robust and reproducible substrate were available. Gold nanoparticles (Au NPs) larger than 20 nm diameter are expected to greatly enhance Raman intensity if they can be assembled into ordered monolayers. A three-phase self-assembly method is presented that successfully results in ordered Au NP monolayers for particle diameters ranging from 13 to 90 nm. The monolayer structure and Raman enhancement factors (EFs) are reported for a model analyte, rhodamine, as well as the best performing polymer electrolyte salt, lithium bis(trifluoromethane)sulfonimide. Experimental EFs for the most part correlate with predictions based on monolayer geometry and with numerical simulations that identify local electromagnetic field enhancements. Lastly, the EFs for the best performing Au NP monolayer are between 106 and 108 and give quantitative signal response when analyte concentration is changed.

Research Organization:
Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States)
Sponsoring Organization:
USDOE Laboratory Directed Research and Development (LDRD) Program
Grant/Contract Number:
AC05-00OR22725
OSTI ID:
1350946
Journal Information:
ACS Applied Materials and Interfaces, Vol. 9, Issue 15; ISSN 1944-8244
Publisher:
American Chemical Society (ACS)Copyright Statement
Country of Publication:
United States
Language:
English
Citation Metrics:
Cited by: 87 works
Citation information provided by
Web of Science

References (79)

Raman spectra of pyridine adsorbed at a silver electrode journal May 1974
Probing Single Molecules and Single Nanoparticles by Surface-Enhanced Raman Scattering journal February 1997
Surface-Enhanced Raman Scattering Study on Passivating Films of Ag Electrodes in Lithium Batteries journal August 2000
Surface- and Tip-Enhanced Raman Spectroscopy in Catalysis journal April 2016
Gold Nanoparticle Based Label-Free SERS Probe for Ultrasensitive and Selective Detection of Trinitrotoluene journal September 2009
Design of SERS-Encoded, Submicron, Hollow Particles Through Confined Growth of Encapsulated Metal Nanoparticles journal January 2009
Gold nanoparticle-packed microdisks for multiplex Raman labelling of cells journal January 2014
Surface-Enhanced Raman Spectroscopy of DNA journal April 2008
Biosensing with plasmonic nanosensors journal June 2008
Surface-Enhanced Raman Spectroscopy Applied to Food Safety journal February 2013
Surface-Enhanced Raman Spectroscopy journal July 2008
Gold Nanoparticle Monolayers with Tunable Optical and Electrical Properties journal April 2016
Nanostructured Surfaces and Assemblies as SERS Media journal October 2008
Inverted Size-Dependence of Surface-Enhanced Raman Scattering on Gold Nanohole and Nanodisk Arrays journal July 2008
Isolating Surface-Enhanced Raman Scattering Hot Spots Using Multiphoton Lithography journal October 2009
Nanohole-Enhanced Raman Scattering journal September 2004
Highly Reproducible and Sensitive SERS Substrates with Ag Inter-Nanoparticle Gaps of 5 nm Fabricated by Ultrathin Aluminum Mask Technique journal June 2015
Controlled assembly of plasmonic colloidal nanoparticle clusters journal January 2011
Assemblies of silver nanocubes for highly sensitive SERS chemical vapor detection journal January 2013
Self-assembly of large-scale crack-free gold nanoparticle films using a ‘drain-to-deposit’ strategy journal April 2016
Large-Scale Uniform Two-Dimensional Hexagonal Arrays of Gold Nanoparticles Templated from Mesoporous Silica Film for Surface-Enhanced Raman Spectroscopy journal October 2016
Assembly of Highly Ordered Nanoparticle Monolayers at a Water/Hexane Interface journal October 2007
Large-Scale Hot Spot Engineering for Quantitative SERS at the Single-Molecule Scale journal October 2015
Self-Assembled Metal Colloid Monolayers: An Approach to SERS Substrates journal March 1995
Evaporation-induced self-assembly of gold nanoparticles into a highly organized two-dimensional array journal November 2002
Directing Cluster Formation of Au Nanoparticles from Colloidal Solution journal February 2013
Assembly of Colloidal Crystals at Electrode Interfaces journal November 1997
Langmuir−Blodgett Monolayers of Gold Nanoparticles with Amphiphilic Shells from V-Shaped Binary Polymer Arms journal August 2006
Kinetically driven self assembly of highly ordered nanoparticle monolayers journal March 2006
Structure and Dynamics in Alkanethiolate Monolayers Self-Assembled on Gold Nanoparticles:  A DSC, FT-IR, and Deuterium NMR Study journal March 1997
Self-Organization of Large Gold Nanoparticle Arrays journal August 2001
Anisotropic Metal Nanoparticles for Use as Surface-Enhanced Raman Substrates journal July 2007
Tunable Surface-Enhanced Raman Scattering from Large Gold Nanoparticle Arrays journal December 2001
Single-Molecule Surface-Enhanced Raman Spectroscopy journal May 2012
Directing Close-Packing of Midnanosized Gold Nanoparticles at a Water/Hexane Interface journal March 2008
Particle size dependence of the surface-enhanced Raman scattering properties of densely arranged two-dimensional assemblies of Au(core)–Ag(shell) nanospheres journal January 2015
Densely arranged two-dimensional silver nanoparticle assemblies with optical uniformity over vast areas as excellent surface-enhanced Raman scattering substrates journal January 2013
Controlling dynamic SERS hot spots on a monolayer film of Fe3O4@Au nanoparticles by a magnetic field journal January 2016
Gold Nanoparticle Monolayers from Sequential Interfacial Ligand Exchange and Migration in a Three-Phase System journal October 2016
Spontaneous Assembly of a Monolayer of Charged Gold Nanocrystals at the Water/Oil Interface journal January 2004
Understanding the self-assembly of charged nanoparticles at the water/oil interface journal January 2006
Particles as surfactants—similarities and differences journal March 2002
Two-Dimensional Interfacial Colloidal Crystals journal August 1980
The Surface Tension of Pure Liquid Compounds journal October 1972
Resonant Field Enhancements from Metal Nanoparticle Arrays journal January 2004
Plasmon Hybridization in Nanoparticle Dimers journal May 2004
On the Universal Scaling Behavior of the Distance Decay of Plasmon Coupling in Metal Nanoparticle Pairs: A Plasmon Ruler Equation journal July 2007
Gold nanoparticles: Optical properties and implementations in cancer diagnosis and photothermal therapy journal January 2010
In Situ Localized Surface Plasmon Resonance (LSPR) Spectroscopy to Investigate Kinetics of Chemical Bath Deposition of CdS Thin Films journal February 2015
Calculated Absorption and Scattering Properties of Gold Nanoparticles of Different Size, Shape, and Composition:  Applications in Biological Imaging and Biomedicine journal April 2006
Beiträge zur Optik trüber Medien, speziell kolloidaler Metallösungen journal January 1908
Optical scattering resonances of single and coupled dimer plasmonic nanoantennas journal January 2007
Strong Enhancement of the Radiative Decay Rate of Emitters by Single Plasmonic Nanoantennas journal September 2007
Shedding light on dark plasmons in gold nanorings journal June 2008
A subwavelength plasmonic metamolecule exhibiting magnetic-based optical Fano resonance journal January 2013
Nanomanipulation and controlled self-assembly of metal nanoparticles and nanocrystals for plasmonics journal January 2016
Surface-enhanced Raman scattering journal January 1998
Reduction of Fluorescence Interference in Raman Spectroscopy via Analyte Adsorption on Graphitic Carbon journal December 1994
Physics of single molecule fluctuations in surface enhanced Raman spectroscopy active liquids journal November 2004
Rigorous justification of the |E|4 enhancement factor in Surface Enhanced Raman Spectroscopy journal May 2006
A General Strategy for Self-Assembly of Nanosized Building Blocks on Liquid/Liquid Interfaces journal April 2012
Superhydrophobic Surface-Enhanced Raman Scattering Platform Fabricated by Assembly of Ag Nanocubes for Trace Molecular Sensing journal October 2013
Interfacial liquid-state surface-enhanced Raman spectroscopy journal July 2013
Spectroscopic and Theoretical Study of (CF 3 SO 2 ) 2 N - (TFSI - ) and (CF 3 SO 2 ) 2 NH (HTFSI) journal May 1998
Characterization of the Lithium Surface in N-Methyl-N-alkylpyrrolidinium Bis(trifluoromethanesulfonyl)amide Room-Temperature Ionic Liquid Electrolytes journal January 2006
Vibrational study of the structural phase transition in bis(pyrrolidinium)-chloride-hexachloroantimonate(V) by infrared spectroscopy journal September 2002
Rhodamine 6G conjugated to gold nanoparticles as labels for both SERS and fluorescence
studies on live endothelial cells journal June 2014
Solvation Structure around the Li + Ion in Mixed Cyclic/Linear Carbonate Solutions Unveiled by the Raman Noncoincidence Effect journal July 2015
A perspective on single molecule SERS: current status and future challenges journal January 2008
The Extinction Spectra of Silver Nanoparticle Arrays:  Influence of Array Structure on Plasmon Resonance Wavelength and Width journal July 2003
Effects of the Substrate Refractive Index, the Exciting Light Propagation Direction, and the Relative Cube Orientation on the Plasmonic Coupling Behavior of Two Silver Nanocubes at Different Separations journal June 2016
Surface-enhanced Raman spectroscopy: a brief retrospective journal January 2005
Mapping the Plasmon Resonances of Metallic Nanoantennas journal February 2008
Electromagnetic contributions to single-molecule sensitivity in surface-enhanced Raman scattering journal September 2000
A convenient phase transfer protocol to functionalize gold nanoparticles with short alkylamine ligands journal December 2015
A study of the nucleation and growth processes in the synthesis of colloidal gold journal January 1951
Seeded Growth Synthesis of Uniform Gold Nanoparticles with Diameters of 15−300 nm journal February 2011
A Novel Method to Analyze Electromagnetic Scattering of Complex Objects journal November 1982
Plasma resonance enhancement of Raman scattering by pyridine adsorbed on silver or gold sol particles of size comparable to the excitation wavelength journal January 1979

Cited By (16)

Probing Electrolyte Solvents at Solid/Liquid Interface Using Gap-Mode Surface-Enhanced Raman Spectroscopy journal January 2019
Structural and photocatalytic properties of silicon carbide powder and nanowires modified by gold nanoparticles journal June 2019
Natural Deposition Strategy for Interfacial, Self-Assembled, Large-Scale, Densely Packed, Monolayer Film with Ligand-Exchanged Gold Nanorods for In Situ Surface-Enhanced Raman Scattering Drug Detection journal February 2018
Citrate-assisted galvanic replacement for fabrication of homogeneous Ag nanosheets as high-performance SERS substrate journal July 2019
Reliable and quantitative SERS detection of dopamine levels in human blood plasma using a plasmonic Au/Ag nanocluster substrate journal January 2018
A tip–gap mesh-like bilayer SERS substrate for highly sensitive detection journal January 2018
Interferometric time- and energy-resolved photoemission electron microscopy for few-femtosecond nanoplasmonic dynamics journal September 2019
Broadband high responsivity large-area plasmonic-enhanced multilayer MoS 2 on p-type silicon photodetector using Au nanostructures journal September 2019
Recent Advances in 2D Inorganic Nanomaterials for SERS Sensing journal February 2019
Hierarchical Au nanoclusters electrodeposited on amine-terminated ITO glass as a SERS-active substrate for the reliable and sensitive detection of serotonin in a Tris-HCl buffer solution journal January 2019
Application of Gold Nanoparticle to Plasmonic Biosensors journal July 2018
Assembly of gold nanoparticles using turnip yellow mosaic virus as an in-solution SERS sensor journal January 2019
Scaling Laws for Polymer Chains Grafted onto Nanoparticles journal February 2018
Preparation of Gold Nanocomposites with Tunable Charge and Hydrophobicity via the Application of Polymer/Surfactant Complexation journal December 2017
Simple, Low-Cost Fabrication of Highly Uniform and Reproducible SERS Substrates Composed of Ag–Pt Nanoparticles journal May 2018
Seed-Mediated Electroless Deposition of Gold Nanoparticles for Highly Uniform and Efficient SERS Enhancement journal February 2019