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Research Papers

Electric-Field Enhanced Molecule Detection in Suspension on Assembled Plasmonic Arrays by Raman Spectroscopy

[+] Author and Article Information
Chao Liu

Materials Science and Engineering Program,
The University of Texas at Austin,
Austin, TX 78712
e-mail: chaoliu2011@utexas.edu

Xiaobin Xu

Materials Science and Engineering Program,
The University of Texas at Austin,
Austin, TX 78712
e-mail: xxu.uta@gmail.com

D. L. Fan

Materials Science and Engineering Program;
Department of Mechanical Engineering,
The University of Texas at Austin,
Austin, TX 78712
e-mail: dfan@austin.utexas.edu

1Corresponding author.

Manuscript received February 1, 2015; final manuscript received May 29, 2015; published online July 1, 2015. Assoc. Editor: Jianping Fu.

J. Nanotechnol. Eng. Med 5(4), 040906 (Nov 01, 2014) (6 pages) Paper No: NANO-15-1011; doi: 10.1115/1.4030769 History: Received February 01, 2015; Revised May 29, 2015; Online July 01, 2015

One of the greatest challenges in surface enhanced Raman scattering (SERS) sensing is to detect biochemicals directly from suspension with ultrasensitivity. In this work, we employed strategically designed longitudinal nanocapsule structures with uniformly surface distributed Ag nanoparticles (Ag NPs) to dually focus and enhance SERS sensitivity of biochemicals in suspension assisted with electric fields. By tuning the reaction conditions, Ag NPs were synthesized and uniformly grown with optimized sizes and junctions on the surface of nanocapsules for well reproducible detection. The Ag NPs can further concentrate molecules from suspension due to induced electrokinetic effects in electric fields. As a result, the signals of Nile blue molecules can be enhanced by 34.4±3.1% at optimal alternating current (AC) frequencies and voltages compared to that without electric fields. This work demonstrates the dual roles of a new type of plasmonic NPs for molecule concentration and detection, which could inspire new Raman sensing devices for applications in microfluidics.

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Figures

Grahic Jump Location
Scheme 1

(a) The cross section schematic diagram of a nanocapsule where a metallic Au nanowire serves as the core, a silica layer grown on the surface of the metal core support the Ag NPs growth and Ag NPs uniformly grow on the silica layer. (b) Side view scheme of a nanocapsule.

Grahic Jump Location
Fig. 1

Scanning electron microscopy (SEM) images of (a) arrays of Au nanowires with an average length of 8.5 μm and diameter of 300 nm, (b) Au nanowire encapsulated by a 180 nm thick silica layer, and (c) SEM images of Au/silica nanocapsules coated with Ag NPs (the zoom-in images of Ag NPs are shown in Fig. 2.)

Grahic Jump Location
Fig. 2

SEM images of nanocapsules fabricated at different conditions with reactant concentrations and volumes as: (a) AgNO3 (0.06 M, 350 μl): NH3•H2O (0.12 M, 175 μl), (b) AgNO3 (0.06 M, 400 μl): NH3•H2O (0.12 M, 200 μl), (c) AgNO3 (0.06 M, 500 μl): NH3•H2O (0.12 M, 250 μl), and (d) AgNO3 (0.06 M, 600 μl): NH3•H2O (0.12 M, 300 μl)

Grahic Jump Location
Fig. 3

Raman detection from nanocapsules in 100 μM R-6 G suspension. (a) Well repeatable Raman signals from nanocapsules synthesized in the same batch with volumes of AgNO3 and NH3•H2O as 500 μl: 250 μl. (b) Comparison of Raman signals from samples fabricated at different conditions with volumes of AgNO3 and NH3•H2O as 400 μl: 200 μl (black) 500 μl: 250 μl (red), and 600:300 μl (blue).

Grahic Jump Location
Fig. 4

(a) Schematic diagram of nanocapsules assembled on interdigital microelectrodes, (b) the attraction of molecule to the nanocapsules with the electric fields, (c) Raman image of Nile blue molecules (with background fluorescence of Nile blue molecules and Ag NPs) on arrays of assembled nanocapsules on microelectrodes (enhanced image), and (d) the corresponding optical microscopy image

Grahic Jump Location
Fig. 5

(a) Raman spectrum of Nile blue (250 nM) detected from a nanocapsule in solution, which demonstrated that 595 cm−1 was the most prominent Raman peak and well separated from others. (b) Frequency dependent Raman intensity enhancement at 595 cm−1 of Nile blue molecules (100 nM) recorded after applying an electric field at 20 V and 200 kHz to 1 MHz (the curve in orange is an eye guide.)

Grahic Jump Location
Fig. 6

Time dependent Raman intensity at 595 cm−1 of Nile blue molecules (100 nM) recorded before and after applying an electric field at 200 kHz (a) 5 V, (b) 10 V, (c) 15 V, and (d) 20 V

Grahic Jump Location
Fig. 7

Time dependent Raman intensity of Nile blue molecules (100 nM) at 595 cm−1 recorded when the E-field is turned on and off alternatively at 20 V, 200 kHz

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