Bi-Ju Liu

DNA-Directed Gold Nanodimers with Tunable Sizes and Interparticle Distances and Their Surface Plasmonic Properties

A quantitative understanding of the localized surface plasmon resonances (LSPRs) of metallic nanostructures has received tremendous interest. However, most of the current studies are concentrated on theoretical calculation due to the difficulty in experimentally obtaining monodisperse discrete metallic nanostructures with high purity. In this work, endeavors to assemble symmetric and asymmetric gold nanoparticle (AuNP) dimer structures with exceptional purity are reported using a DNA self-assembly strategy through a one-step gel electrophoresis, which greatly facilitates the preparation process and improves the final purity. In the obtained Au nanodimers, the sizes of AuNPs (13, 20, and 40 nm) and the interparticle distances (5, 10, and 15 nm) are tunable. The size- and distance-dependent plasmon coupling of ensembles of single, isolated dimers in solution are subsequently investigated. The experimental measurements are correlated with the modeled plasmon optical properties of Au nanodimers, showing an expected resonance shift with changing particle sizes and interparticle distances. This new strategy of constructing monodisperse metallic nanodimers will be helpful for building more complicated nanostructures, and our theoretical and experimental understanding of the intrinsic dependence of plasmon property of metallic nanodimer on the sizes and interparticle distances will benefit the future investigation and exploitation of near-field plasmonic properties.

Cu–Au alloy nanotubes with five-fold twinned structure and their application in surface-enhanced Raman scattering

Cu–Au alloy nanostructures have received considerable attention in recent years due to their widespread use in applications such as catalysis, photonics and surface-enhanced Raman scattering (SERS) detection. In this article, a template-based strategy has been developed to synthesize Cu–Au nanotubes with five-fold twinned structure by using Cu nanowires as templates and AuPPh3Cl as Au precursors in the organic phase of oleylamine. It was verified that high quality Cu–Au alloy nanotubes could result from the Cu–Au alloy effect, the Kirkendall effect, and the galvanic replacement reaction. It was also demonstrated that the Cu–Au alloy nanotubes may have potential applications in SERS detection because of their good stability and convenience for building “hot spots”.

Uniform gold spherical particles for single-particle surface-enhanced Raman spectroscopy

Surface-enhanced Raman spectroscopy (SERS) benefits from the enhanced electromagnetic field of the localized surface plasmon resonance effect of metallic (especially coinage metals) nanoparticles or nanostructures. The detection sensitivity and reproducibility of SERS measurement appear to be the two critical issues in SERS. To solve the problem associated with traditional nanoparticle aggregates and SERS substrates, we propose in this work single particle SERS. We prepared uniform gold microspheres with controllable size and surface roughness using an etching-assisted seed-mediated method. Single particle dark-field spectroscopy and SERS measurements show that particles with a larger roughness give a stronger SERS signal, but still retain a good reproducibility. This study points to the promising future of the practical application of the single particle SERS technique for trace analysis.

Plasmonic photoluminescence for recovering native chemical information from surface-enhanced Raman scattering

Surface-enhanced Raman scattering (SERS) spectroscopy has attracted tremendous interests as a highly sensitive label-free tool. The local field produced by the excitation of localized surface plasmon resonances (LSPRs) dominates the overall enhancement of SERS. Such an electromagnetic enhancement is unfortunately accompanied by a strong modification in the relative intensity of the original Raman spectra, which highly distorts spectral features providing chemical information. Here we propose a robust method to retrieve the fingerprint of intrinsic chemical information from the SERS spectra. The method is established based on the finding that the SERS background originates from the LSPR-modulated photoluminescence, which contains the local field information shared also by SERS. We validate this concept of retrieval of intrinsic fingerprint information in well controlled single metallic nanoantennas of varying aspect ratios. We further demonstrate its unambiguity and generality in more complicated systems of tip-enhanced Raman spectroscopy (TERS) and SERS of silver nanoaggregates.

Extraction of Absorption and Scattering Contribution of Metallic Nanoparticles Toward Rational Synthesis and Application

Noble metal nanoparticles have unique localized surface plasmon resonance (LSPR), leading to their strong absorption and scattering in the visible light range. Up to date, the common practice in the selection of nanoparticles for a specific application is still based on the measured extinction spectra. This practice may be erroneous, because the extinction spectra contain both absorption and scattering contribution that may play different roles in different applications. It would be highly desirable to develop an efficient way to obtain the absorption and scattering spectra simultaneously. Herein, we develop a method to use the experimentally measured extinction and scattering signals to extract the absorption and scattering spectra that is in excellent agreement with that simulated by discrete dipole approximation (DDA). The heating curve measurement on the three types of gold nanorods, with almost the same extinction spectra but different absorption and scattering contribution, convincingly reveals an excellent correlation between the heating effect and the absorption strength rather than the extinction strength. The result demonstrates the importance to obtain the scattering and absorption spectra to predict the potential application for different types of nanoparticles, which in turn will screen efficiently nanoparticles for a specific application.