MP07



Code: MP07 Time Slot/Poster Number: 111 Session: SERS (substrate development, single molecule, theory) I

Surface Enhanced Spectroscopy of Organic Molecules Deposited on Nanostructured Gold Surfaces
Alexandre Merlen1; Virginie Chevallier1; Jean Christophe Valmalette1; François Lagugné-Labarthet2; Etienne harté2
1IM2NP-Université du Sud Toulon-Var, La Garde, France; 2University of Western Ontario, London, Canada

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Summary
We have prepared gold nanostructures and studied their SERS and SEF activity. The collected signal was compared with other gold substrates. We have clearly observed a relationship between the optical absorption of the gold nanostructures and the intensity of the SERS signal. Those experimental results are in accordance with the plasmonic model of the electromagnetic enhancement. However the observed SERS signal can be clearly modulated by the classical resonant mechanism. Using Rhodamine we studied the time evolution of both SERS and SEF signals and observed strong similarities suggesting a common mechanism for both SERS and SEF.

Code: MP07 Time Slot/Poster Number: 112 Session: SERS (substrate development, single molecule, theory) I

Electrodeposited Silver Nanoparticles Patterned Hexagonally for SERS
GeunHoi Gu; Sue Yeone Lee; Jung Sang Suh
Nano-materials Lab., Seoul National University, Seoul, South Korea

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Summary
Fabrication of silver nanoparticles by electrodepositing silver on the surface of a patterned aluminum plate was done. When silver was electro-deposited, silver nanoparticles were made along the sides of the hexagons. The average size of silver nanoparticles increased with increasing deposition time. Silver nanoparticles formed hexagonal nano-patterns and they were almost in contact with each other. A good SERS spectrum of p-aminothiophenol was observed by excitation with a 514.5 nm. This highly enhanced signal of SERS might be due to some junction effect of our silver nanoparticles. This substrate could be used to fabricate hot spots for SERS.

Code: MP07 Time Slot/Poster Number: 114 Session: SERS (substrate development, single molecule, theory) I

From Average to Single Molecule Surface Enhanced Raman Scattering
Jeremie Margueritat1; Helene Gehan1; Johan Grand1; Georges Lévi1; Jean Aubard1; Nordin Félidj1; Alexandre Bouhelier2; Gérard Colas-des-Francs2; Laurent Markey2; Carmen Marco de Lucas2; Alain Dereux2; Eric Finot2
1ITODYS, Université Paris7-Denis Diderot, Paris, France; 2LICB, CNRS UMR 5209, Université de Bourgogne, Dijon, France

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Summary
We produce controllable and reproducible SERS active areas by combining chemical immobilization and electron beam lithography. For large areas the SERS intensity is averaged over a large amount of probe molecules (average SERS). On the contrary, for small SERS areas, the signal mainly arises from single molecule events (single molecule SERS). This study demonstrate that average SERS is more suitable for SERS-sensors, while single molecule SERS are particularly suitable to investigate the SERS mechanisms.

Code: MP07 Time Slot/Poster Number: 116 Session: SERS (substrate development, single molecule, theory) I

Two-step Fabrication of Metal-Coated Silicon Nanopillars with Large Raman Enhancement
Michael Stenbæk Schmidt1; Jörg Hübner2; Anja Boisen1
1DTU Nanotech, Technical University of Denmark, Kgs. Lyngby, Denmark; 2DTU Danchip, Technical University of Denmark, Kgs. Lyngby, Denmark

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Summary
Freestanding vertical silicon nanopillars with uniform heights are fabricated by maskless plasma etching. The nanopillar’s heights and density are tuneable and optimized for SERS. The nanopillars are coated with silver and/or gold to facilitate Raman enhancement. Wafer scale surfaces, uniformly covered by nanopillars show large enhancements of a variety of test molecules including dinitrotoluene (DNT). These cost effective substrates are believed to be able to make SERS more applicable for both liquid and gas phase SERS based chemical and biochemical sensors. These substrates will be included in a handheld explosives detector being developed in the Xsense project at DTU.

Code: MP07 Time Slot/Poster Number: 117 Session: SERS (substrate development, single molecule, theory) I

Study on Localized SERS by Spatially Selective Deposition of Raman Analytes
Chang Chen1; Jian Ye1; Ronald Kox1; Francesca Clemente1; Liesbet Lagae1; Guido Maes2; Gustaaf Borghs1; Pol Van Dorpe1
1imec vzw, Leuven, Belgium; 2Katholieke Universiteit Leuven, Leuven, Belgium

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Summary
Localized SERS is important for Raman applications in sensors. However, due to the diffraction limitation of light, investigation on this property is a challenge. Here, We use a modified electron beam inducted deposition process to selectively place Raman analyes in complex 3D SERS substrates such as a plasmonic nanoslit-cavity. The localization of SERS is directly proved and the near-field photochemical degradation in hot spot regions is also studied. We expect it will become an universal and convenient approach for the localized SERS study.

Code: MP07 Time Slot/Poster Number: 118 Session: SERS (substrate development, single molecule, theory) I

SERS-Based Ultrasensitive Detection with Tips-shaped Anisotropic Particles
Laura Rodriguez-Lorenzo1; Paula Aldeanueva-Potel1; Ramon Alvarez-Puebla1; Luis Liz-Marzan1; Javier Garcia de Abajo2
1Universidade de Vigo, Vigo, Spain; 2Instituto de Optica - CSIC, Madrid, Spain

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Summary
Herein, it is reported star-shaped nanoparticles which show electromagnetic field concentration at their tips. As consequence, the SERS in this type of particles, is substantially higher than in spherical particles of similar dimension. This focalization effect is exteded to more complex structures such as thorn-shaped nanowires. Furthermore, it is demostred controllable SERS signal amplification (EF~1010) reaching the zeptomol detection by sandwiching the probed molecules between the tips of star-shaped gold nanoparticles and a planar gold surface.

Code: MP07 Time Slot/Poster Number: 119 Session: SERS (substrate development, single molecule, theory) I

Star-shaped Silver Nanoparticles as SERS Substrates for Trace Analysis of Polycyclic Aromatic Hydrocarbons
Jean Claudio Costa; Paola Corio
University of São Paulo, São Paulo, Brazil

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Summary
We describe in this work the performance of silver nanostars as substrates for SERS study of two polycyclic aromatic hydrocarbons (PAHs), an important class of environmental pollutants formed mainly as a result of the incomplete combustion of organic materials. The investigated analytes are anthracene and 9-nitroanthracene. Density functional theoretical (DFT) calculations for normal Raman and SERS spectra were performed for a reliable analysis of specific molecule-surface interaction and to support the enhancement patterns observed in each SERS spectra.

Code: MP07 Time Slot/Poster Number: 120 Session: SERS (substrate development, single molecule, theory) I

A DFT Study of Surface-Enhanced Raman Spectroscopy of Adenine and Adenine-Silver Complexes
Rong Huang; Liu-Bin Zhao; De Yin Wu; zhong-Qun Tian
State Key Laboratory of Physical Chemistry of Soli, Xiamen, China

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Summary
we report our theoretical results from density functional theory (DFT) calculations on Raman spectra and SERS of adenine, adenine-silver ions and adenine-silver cluster complexes as well as possible surface species from adsorbed adenine.

Code: MP07 Time Slot/Poster Number: 121 Session: SERS (substrate development, single molecule, theory) I

Fabrication of SERS Substrate by Multilayered Nanosphere Deposition Technique
Chit Yaw Fu1; Zhen Yu Koh2; U.S Dinish1; Khiang Wei Kho3; Thoniyot Praveen1; Olivo Malini4
1Bio-Optical Imaging Group, Singapore Bioimaging Co, Singapore, Singapore; 2National University of Singapore, Singapore, Singapore; 3National Cancer Center, Singapore, Singapore; 4National University of Ireland, Galway, Ireland

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Summary
Metal film over nanosphere (MFON) has been employed as a reproducible and predictable SERS-active device in biosensing applications. In addition to its economic fabrication process, such substrate can be further processed to a prism-structure with increased SERS enhancement and wider Plasmon tunability. In this work, we investigate an alternative coating method to deposit a larger area of well-ordered PS beads with different sizes (ø=100nm and 400nm) onto a glass. The result suggests that the proposed well-coating technique can be suitably used to form closely-packed PS beads with diameter less than 100nm for developing MFON substrates.

Code: MP07 Time Slot/Poster Number: 122 Session: SERS (substrate development, single molecule, theory) I

Blinking of SERRS Excited by Various Laser Intensities
Yasutaka Kitahama1; Yuhei Tanaka1; Tamitake Itoh2; Yukihiro Ozaki1
1School of Sci and Tech, Kwansei Gakuin University, Sanda, Japan; 2Health Technology Research Center, AIST, Takamatsu, Japan

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Summary
Blinking statistics in surface-enhanced resonance Raman scattering (SERRS) of thiacarbocyanine adsorbed on single Ag nanoaggregates were analyzed by a power-law that reproduces probability distributions of the dark and bright SERRS occurrences against their duration times. In the dark SERRS occurrences, the line given by the power-law was truncated at the tail. It has been reported that the truncation at the tail of power-law is reproduced by random walk on parabolic potential surfaces against reaction coordinate for emissive and non-emissive states. The truncation times in the dark SERRS were not varied by change of the excitation laser intensity.

Code: MP07 Time Slot/Poster Number: 123 Session: SERS (substrate development, single molecule, theory) I

Aperiodic Plasmonic Platforms for Multi-Parametric Sensing and Spectroscopy
Svetlana Boriskina; Sylvanus Lee; Bo Yan; Björn Reinhard; Luca Dal Negro
Boston University, Boston, MA

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Summary
We will report on the design and applications of aperiodic plasmonic nano-structures that simultaneously provide broadband near-field enhancement and narrow-linewidth resonant features in their far-field scattering spectra. The unique scattering and field localization characteristics of aperiodic plasmonic arrays pave the way for their use as broadband multiplexed sensing platforms for multiple and unspecified molecular targets. In such platforms, the presence of the analyte can be detected by tracing the shifts of the narrow resonant features, and fingerprinting of molecular targets can be done by probing their Raman and/or fluorescence spectra across a wide frequency range in the visible and near-infrared.

Code: MP07 Time Slot/Poster Number: 124 Session: SERS (substrate development, single molecule, theory) I

Comparison of the Performance of SERS Substrates Fabricated by Deep UV Lithography and Nanosphere Lithography
Dinish U S1; Ajay Agarwal2; Fu Chit Yaw1; Malini Olivo1
1Singapore Bioimaging Consortium, 11 Biopolis Way, Singapore; 2Institute of Microelectronics, Singapore Science Park 2, Singapore

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Summary
Performance of SERS substrates fabricated by nanosphere lithography (NSL), deep UV (DUV) lithography and also a commercial substrate is analyzed by studying its reproducibility, repeatability and signal enhancement capability. It was found that NSL substrate shows stronger enhancement but the intensity variation for the two prominent peaks of napthalenethiol is about 7-14% while for the DUV substrate it is less than 5%. Also, these two substrates have shown much better performance compared to the commercial substrate. The smaller variation in intensity achieved with DUV substrate is remarkable and shows the great potential of it for sensitive SERS based biosensing.

Code: MP07 Time Slot/Poster Number: 125 Session: SERS (substrate development, single molecule, theory) I

Analysis of SERS Reproducibility on Nanoparticle Microarrays
Michele De Souza1; Milton Wang2; Paola Corio1; Alexandre Brolo2
1Universidade de São Paulo, São Paulo, Brazil; 2University of Victoria, Victoria, Britsh Columbia

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Summary
The hotspots are known to be difficult to control and reproduce, reducing the applicability of SERS in bioanalytical and analytical chemistry. It is thus desirable to find a way of creating and controlling the electromagnetic amplifications in a more consistent and reproducible manner. Here we proposed the use of microfluidics for the chemical immobilization of metallic nanoparticles on glass, creating patterned SERS microarrays for analytical applications. The technique reported here has shown great potential for ultrasensitive detection of biological molecules.

Code: MP07 Time Slot/Poster Number: 126 Session: SERS (substrate development, single molecule, theory) I

A Highly Reproducible SERS Detection of Biomolecules Using Lithographied Nanoparticles : Application to Biosensors
Catalina David1; Nicolas Guillot1; Hong Shen2; Timothee Toury2; Marc Lamy de la Chapelle1
1University Paris 13, Bobigny, France; 2Université de technologie de Troyes, 10010 Troyes, France

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Summary
The purpose of the present study is to achieve a SERS sensor with extreme sensitivity and very high molecular specificity by combining the enhancement of vibrational signal, surface functionalization, respectively, and detection of vibrational Raman spectra signals in order to provide at very low concentration the spectral signature of proteins. Our SERS sensor is based on gold nanocylinder arrays obtained by Electron Beam lithography. Our preliminary results concern the first study of SERS efficiency of nanocylinder arrays at 632 nm in the case of proteins, BSA and RNAse. The maximum SERS intensity obtained for a specific nanocylinder diameter (100nm).

Code: MP07 Time Slot/Poster Number: 127 Session: SERS (substrate development, single molecule, theory) I

Physical Method to Shape A Nano-Structured Au Substrate for Surface Enhanced Raman Scattering
Ying Yi Lin1, 1; Jiunn-Der Liao1, 2; Yu-Hung Chu1, 2
1, Tainan, TAIWAN; 2National Cheng Kung University, Tainan, Taiwan

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Summary
In this study, Dual-Beam Focused Ion Beam (DB-FIB) is applied for the fabrication of nano-structured and patterned SERS-active surfaces. The optimized condition to detect trace amount of R6G molecules was measured as followed: fibAu dimension of 150nm and laser wavelength of 633 nm. Based on the measurement, the enhancement factors was optimized at 107. In addition, the dimension increased with lower Raman intensity owing to a larger dimension tends to get little space, which contains fewer molecules in detection area.

Code: MP07 Time Slot/Poster Number: 128 Session: SERS (substrate development, single molecule, theory) I

Revelation Of Molecular Information Obtained From Porous Al2O3 Substrates Applying Polarized SERS
Kit D. Jernshøj; Søren Hassing; Rene S. Hansen; Peter Nielsen
Sense Institute, Faculty of Engineering, Universit, Odense, Denmark

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Summary
When the goal of applying SERRS is to obtain molecular information one must explain the difference often seen between resonance Raman and SERRS spectra. Recently, we have shown that vital molecular information does not survive, when the molecule is physisorbed in a highly anisotropic hot spot. Here we consider a porous Al2O3 substrate with a highly symmetric structure containing both isotropic and anisotropic sites. The polarization properties of SERRS obtained from a monolayer of R6G-molecules, adsorbed to the substrate are measured. It is concluded that the dominating scattering contribution comes from R6G molecules adsorbed to the anisotropic sites.

Code: MP07 Time Slot/Poster Number: 129 Session: SERS (substrate development, single molecule, theory) I

Surface-Enhanced Raman Scattering of Hydroxyproline in Gold Colloids
Ariel Guerrero; Ricardo Aroca
University of Windsor, Windsor, Canada

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Summary
In this work, we have employed hydroxyproline as our problem molecule, and tackled the problem of reproducibility by employing gold colloids instead of the usual silver to achieve SERS. We concentrated the gold particles by centrifuging the colloid at 14000 rpm by 7 minutes. The SERS spectra show distinctive bands of hydroxyproline, assigned by comparison to normal Raman spectra and DFT calculations. Repeated measurements using this procedure showed no significant variation in the spectra obtained.

Code: MP07 Time Slot/Poster Number: 130 Session: SERS (substrate development, single molecule, theory) I

Concentration and pH-dependent SERS study of 2-Marcaptoimidazole adsorbed on colloidal silver nano particles
Subhendu Chandra
Indian Association for the Cultivation of Science, Kolkata, India

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Summary
We report the Normal Raman (NR), FTIR and Surface enhanced Raman scattering (SERS) of 2-Marcaptoimidazole molecule adsorbed on nano colloidal silver surface. Concentration dependent SERS spectral profile reveal maximum enhancement of the overall SERS signal of the probe molecule at a concentration of ~10-3 M. SER spectra of 2-Marcaptoimidazole molecule recorded at different pH values at an adsorbate concentration of 10−3 M

Code: MP07 Time Slot/Poster Number: 131 Session: SERS (substrate development, single molecule, theory) I

Tunable Surface Enhanced Raman Scattering from Aluminum Nanohole Arrays
Zhi-Lin Yang1; Qian-Hong Li1; De-Yin Wu2; Bin Ren2; Zhong-Qun Tian2
1Department of Physics, Xiamen University, Xiamen,, Xiamen, China; 2Department of Chemistry, Xiamen University, Xiamen, xiamen, xiamen

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Summary
Ordered aluminum nanohole arrays for tunable surface enhanced Raman scattering (SERS) in the ultraviolet (UV) region is proposed and studied theoretically. Both optical transmission spectra and local field enhancement in this structure with various hole periodicities were simulated based on the three dimensional finite difference time domain (3D-FDTD) method. The key finding in this work is that properly designed Al nanohole arrays produce stable and predictable SERS enhancement under near UV and even deep UV laser illumination, and the surface enhancement factor can be as high as 4 to 5 orders in the optimum geometry structure.

Code: MP07 Time Slot/Poster Number: 133 Session: SERS (substrate development, single molecule, theory) I

High-Density Periodic Arrays of Subwavelength Nanopyramids for Surface Enhanced Raman Scattering
Mingliang Jin1; Vishnu Pully2; Cees Otto2; Albert Van den Berg1; Edwin T. Carlen1
1BIOS/Lab-on-chip group, MESA+Institute, Enschede, The Netherlands; 2Medical Cell BioPhysics Group, MESA+ Institute, Enschede, The Netherlands

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Summary
We present novel large area ~100 µm2 nanotextured surfaces consisting of densely packed nanopyramids and nanogrooves with nearly atomically precise sizes and spacing. The new nano-pyramid surfaces are ideally suited for SERS as the lateral and vertical dimensions can be varied from 200 nm down to ~50 nm, with any suitable plasmonic layer, such as Ag or Au, and contain a large density of hot-spots located at the base of the closely spaced nanopyramids and nanogrooves.

Code: MP07 Time Slot/Poster Number: 134 Session: SERS (substrate development, single molecule, theory) I

Surface-Enhanced Raman Scattering –Active Surfaces Based on Au-coated GaN
Agnieszka Kaminska
Institute of Physical Chemistry PAN, Warsaw, Poland

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Summary
Although a number of excellent recent reviews have discussed the considerable progress that has been made towards improving and optimizing SERS substrates [2], a fabrication-reproducible SERS platform still remains a challenging task. Construction of ultra-sensitive and highly reproducible SERS-platforms is very important in developing a practical SERS sensor for efficient biological and medical applications [3]. Here we present a SERS-active platform based on Au-coated porous GaN. Au film was deposited by thermal vacuum evaporation. SERS spectra of Malachite green isothiocyanate ( MGITC) and p-aminothiophenol were recorded at =632.8 nm.