Two types of core/shell nanoparticles (CS-NPs) generation based on laser ablation are developed in this study, namely, double pulse laser ablation and laser ablation in colloidal solutions. In addition to the study of the generation mechanism of CS-NPs in each scheme, the optical properties of designed CS-NPs are determined with UV-VIS-NIR spectroscopy and EM field simulation. In the first scheme, which is double pulse laser ablation, two laser beams are fired in a sequence on two adjacent targets with different material. We have successfully demonstrated the generation of Sn/Glass, Zn/Glass, Zn/Si, Ge/Si, and Cu/Zn CS-NPs. Key factors affecting the generation of CS-NPs are (1) surface tensions of the constructing materials affecting the associated Gibbs free energy of CS-NPs, (2) physical properties of selected background gases (i.e., He and Ar), (3) delay time between two laser pulses, and (4) the amount of laser energy. The second scheme examined for the generation of CS-NPs is through laser ablation of solid targets in colloidal solutions. Compared to the double pulse laser ablation, this second approach provides better control of the size and shape of the resulting CS-NPs. Two colloidal solutions, namely, Au and SiO2 colloidal solution are applied in the second scheme. Key factors affecting the formation of CS-NPs with the second scheme and are (a) the adhesion energy between the shell and the core material, (b) the diameter of the core and (c) the laser ablation time and the laser energy. Red shift of absorption peaks are measured in both SiO2/Au and SiO2/Ag colloids compared with pure nanoparticles (NPs). The amount of red-shift is very sensitive to the shell thickness of the CS-NPs. The same red shift is reproduced with the corresponding full wave analysis. The observed red shift can be attributed to the additional surface plasmon resonance at the interface of metal/dielectric of the CS-NPs compared with pure nanoparticles. Through adjusting the material and size combination, the absorption peak of the CS-NPs can be tuned in a limit range around the intrinsic absorption peak of the metal of the CS-NPs. The freedom of adjusting the absorption peak makes CS-NPs is favorable in bio and optical applications.

Diss. (sammanfattning) Linköping : Univ., 2001. / Härtill 6 uppsatser.

Dissertation (Ph.D.)--Auburn University, 2008. / Abstract. Vita. Includes bibliographic references.

Chemnitz, Techn. Univ., Diss., 1998.

Thesis (Ph. D.)--University of Washington, 2006. / Vita. Includes bibliographical references (leaves 114-127).

Thesis (Ph. D.)--University of Washington, 2007. / Vita. Includes bibliographical references (leaves 228-245).

Thesis (Ph. D.)--University of Washington, 2007. / Vita. Includes bibliographical references (leaves 246-276).

Orientador: Valber de Albuquerque Pedrosa / Resumo: O desenvolvimento de novos dispositivos para monitorar o metabolismo celular e o diagnóstico de doenças expandiu as pesquisas com biossensores, que aliados à nanotecnologia possibilitaram a criação de novos elementos com alta sensibilidade de detecção, especificidade e capacidade de multiplexação, mostrando grande potencial para sua aplicabilidade no diagnóstico clínico. O trabalho foi desenvolvido em duas etapas. A primeira, referiu-se no desenvolvimento de uma metodologia para acoplar o aptâmero conjugado com as nanopartículas de ouro sobre o sensor da Ressonância Plasmônica de Superfície (SPR). Foi utilizado MUA para formação das monocamadas auto-organizadas; ativação dos grupos carboxílicos utilizando solução de EDC/NHS e a imobilização do aptâmero conjugado. Após este processo, foram realizadas as injeções de Mucina Epitelial Polimórfica tipo 1 (MUC1). A segunda etapa, consistiu na mesma metodologia de acoplamento do aptâmero, porém substituindo a MUC1 por sobrenadante da linhagem celular LNCaP (células prostáticas tumorais). Desse modo, foi desenvolvida uma metodologia analítica utilizando aptâmeros e biomarcadores para diagnosticar o Câncer de Próstata (PCa) através da SPR. / Mestre

Plasmon coupling is known to cause distance dependent red-shifts of the characteristic plasmon resonance and localize strong electric fields to the gap between individual nanoparticles. These effects form the basis of nanoscale plasmonic sensors designed by creating specic structures of coupled nanoparticles. The simplest of these structures, a nanoparticle dimer, can easily be assembled through molecular self-assembly, resulting in a structure called a plasmon ruler. These plasmon rulers are crucial tools for the measurement of nanoscale distances, but the impact of the molecular linker on the plasmonic response of the coupled system remains insufficiently understood. In this dissertation, plasmons rulers composed of 40 nm gold nanoparticles are utilized to systematically investigate the potential effects of one molecular linker, DNA, on the strength of the plasmon coupling at a variety of interparticle separations. The strength of the plasmon coupling is determined based on the shifting of the plasmon resonance, which, at separations below 2.7 nm, is significantly blue-shifted when compared to expected values from electromagnetic simulations and experiments without DNA linkers. This deviation indicates a reduced charge accumulation on the nanoparticles in the gap region and is ascribed to DNA-mediated charge transfer. Enhancements to the charge transfer capabilities of the DNA were also investigated, through the deposition of interstitial palladium nanocrystals on the DNA linkers. The deposition of these nanocrystals results in a variety of structural changes to the plasmon rulers, associated with blue- and red-shifts of the plasmon resonance relative to electromagnetic simulations without gap material and experimental spectra of structures without molecular or metallic linkers. The relative blue-shift of the resonance results from a variety of scenarios, including short interparticle separations bridged by DNA or palladium nanocrystals, the build-up of palladium nanocrystals within the gap, or the incorporation of discrete palladium nanoparticles in the DNA linkers. The underlying mechanisms of the observed spectral shifts are analyzed. The red-shifted resonances resulted from a significant build-up of palladium nanocrystals in the gap, effectively linking the gold nanoparticles and forming a hybrid nanorod-like structure.

Surface plasmon is the quantized collective oscillation of the free electron gas in a metallic material. By coupling surface plasmons with photons in different nanostructures, researchers have found surface plasmon polaritons (SPP) and localized surface plasmon resonance (LSPR), which are widely adopted in biosensing, single molecule sensing and detection via surface enhanced raman scattering (SERS), photothermal ablation treatments for cancer, optical tagging and detection, strain sensing, metamaterials, and other applications. The overall objective of this dissertation is to investigate both how mechanics impacts the optical properties, and also how optics impacts the mechanical properties of metal nanostructures reversely. Mechanically engineering individual nanostructures(forward coupling) offers the freedom to alter the optical properties with more flexibility and tunability. It is shown that elastic strain can be applied to gold nanowires to reduce the intrinsic losses for subwavelength optical signal processing, leading to an increase of up to 70% in the surface plasmon polariton propagation lengths at resonance frequencies. Apart from strain engineering, defects are another important aspect of mechanically engineering nanoscale materials, whose impacts on the optical properties of metal nanostructures remain unresolved. An atomic electrodynamic model has been derived to demonstrate that those effects are crucial for ultrasmall nanoparticles with characteristic sizes around 2 nm, and can be safely ignored for those larger than about 5 nm due to the important contribution of nanoscale surface effects. Another key focus of this research project (reverse coupling) is to investigate the currently unknown effects that an external optical field has on the mechanical properties of metal nanostructures. Since each atom in the nanostructure acts as a dipole due to induced electron motions, this optical excitation introduces additional dipolar forces that add to the standard mechanical atomic interactions, which could alter the mechanical properties of the nanostructures. Furthermore, it is shown that when linking mechanics with LSPR, because the metal is dispersive, the mechanical behavior or the strength of the nanostructure should be dependent on the frequency of the electromagnetic excitation. To study this phenomenon, a simpler case with an electrostatic field excitation is considered first, and conclusions are reached on how static fields can be used to tune the elasticity of metallic nanostructures with different sizes and axial orientations and surfaces. Then building upon those understandings, studies were carried out in determining the effects of an optical field, specifically at LSPR frequency, on the mechanical properties of metallic nanostructures. It is found that the initial relaxation strain induced by the static field or optical field is the key factor leading to the variations in the stiffness of the metallic nanostructures that are excited by optical fields at the LSPR frequencies.