In recent years, the Surface Plasmon Polariton effect has played an important role for entering the Nano-world. When the metallic materials reach the nanometer level, many special characteristics show up. As the progress of advanced technology development, the equipments which can be operated in nano grade level are more stabilized. Many special surface Plasmonic properties have been discovered through the measurements. This research is to focus on using the Surface Plasmon coupling to excite colloidal quantum dots and observing the emissive behavior of quantum dots. The experiments of changing the distance between the quantum dots and the metal film were performed. The blinking effect disappeared when the quantum dots are very close to the metal film. It showed that some other mechanism is competing with Auger recombination in the quantum dots. The lifetime modification and emission intensity were measured when one quantum dot was placed near a silver cube. The coupling between the surface Plasmon polariton and the quantum dot was discussed.

京都大学 / 0048 / 新制・課程博士 / 博士(工学) / 甲第18979号 / 工博第4021号 / 新制||工||1619(附属図書館) / 31930 / 京都大学大学院工学研究科マイクロエンジニアリング専攻 / (主査)教授 鈴木 基史, 教授 木村 健二, 教授 蓮尾 昌裕 / 学位規則第4条第1項該当 / Doctor of Philosophy (Engineering) / Kyoto University / DFAM

When exposed to light, metal nanoparticles exhibit a phenomenon known as LSPR, Localized Surface Plasmon Resonance. The wavelengths at which LSPR occurs is very dependent on the refractive index of the surrounding medium. Binding of biomolecules to the surface of gold nanoparticles result in a change in the refractive index that can be detected spectrophotometrically by monitoring the LSPR peak shift. When functionalized with the corresponding ligand(s), gold nanoparticles can be utilized in biosensors to detect the presence and concentration of a predetermined analyte. However, the system must exhibit high specificity and give rise to a detectable shift for analytes in the desired concentration range to be of commercial interest. The aim of the diploma project was to investigate and optimize the biofunctionalization and performance of a fiber optics based LSPR biosensor.  Three ligand systems were investigated for detection of antibodies (IgG), insulin and avidin. Binding of the analyte to the ligand caused a shift of a few nanometers when using spherical gold nanoparticles. The shifts were significantly larger when using gold nanorods. When using the IgG and insulin ligands, only minor unspecific binding was observed. The setup thus shows great potential for use in a wide range of sensing applications.

This dissertation comprises experimental studies on the synthesis and applications of metallic nanoshells. These are a class of nanoparticles composed of a dielectric core and a thin metallic shell. Metallic nanoshells play an important role in nanotechnology, particularly in nanomedicine, due to their peculiar optical properties. The overall objectives of the dissertation were to improve the fabrication of these nanoparticles, and to demonstrate new applications of these materials in cancer research and spectroscopy. The fabrication of nanoshells is a multi-step process. Previously to our work, the procedures for the synthesis of nanoshells reported in the literature lacked systematic characterization of the various steps. The procedure was extremely time-consuming and the results demonstrated a high degree of size variation. In Chapter 3, we have developed characterization tools that provide checkpoints for each step of the synthesis. We demonstrated that it is possible to control the degree of coverage on the shell for a fixed amount of reagents, and also showed important differences on the shell growth phase for gold and silver. The synthetic optimization presented in Chapter 3 led to an overall faster protocol than those previously reported. Although the improvements presented in Chapter 3 led to a higher degree of control on the synthesis of nanoshells, the variations in the resulting particle population were still too large for applications in single particle spectroscopy and imaging. In Chapter 4, the synthesis was completely reformulated, aiming to narrow the size distribution of the nanoshell colloids. Through the use of a reverse microemulsion, we were able to fabricate ultramonodisperse silica (SiO2) cores, which translate into nanoshell colloids with narrow extinction bands that are comparable to those of a single nanoshell. We then fabricate a library of colloids with different core sizes, shell thicknesses and composition (gold or silver). The localized surface plasmon resonance (LSPR) of these colloids span across the visible range. From this library, two nanoshells (18nm silver on a 50nm SiO2 core, and 18nm gold on a 72nm SiO2 core) were selected for a proof of principle cell imaging experiment. The silver nanoshells were coated with a nuclear localization signal, allowing it to target the nuclear membrane. The gold nanoshells were coated with an antibody that binds to a receptor on the plasma membrane of MCF-7 human breast cancer cells. The nanoshells were easily distinguishable by eye in a dark field microscope and successful targeting was demonstrated by hyperspectral dark field microscopy. A comparison was made between fluorescent phalloidin and nanoshells, showing the superior photostability of the nanoparticles for long-term cell imaging. The results from Chapter 4 suggest that the nanoshells obtained by our new synthetic route present acceptable particle-to-particle variations in their optical properties that enables single particle extinction spectroscopy for cell imaging. In Chapter 5 we explored the use of these nanoshells for single-particle Surface-enhanced Raman spectroscopy (SERS). Notice that particle-to-particle variations in SERS are expected to be more significant than in extinction spectroscopy. This is because particle-to-particle SERS variabilities are driven by subtle changes in geometric parameters (particle size, shape, roughness). Two types of gold nanoshells were prepared and different excitation wavelengths (λex) were evaluated, respective to the LSPR of the nanoshells. Individual scattering spectra were acquired for each particle, for a total of 163 nanoshells, at two laser excitation wavelengths (632.8 nm and 785 nm). The particle-to-particle variations in SERS intensity were evaluated and correlated to the efficiency of the scattering at the LSPR peak. Chapter 6 finally shows the application of gold nanoshells as a platform for the direct visualization of circulating tumor cells (CTCs). 4T1 breast cancer cells were transduced with a non-native target protein (Thy1.1) and an anti-Thy1.1 antibody was conjugated to gold nanoshells. The use of a transduced target creates the ideal scenario for the assessment of nonspecific binding. On the in vitro phase of the study, non-transduced cells were used as a negative control. In this phase, parameters such as incubation times and nanoshell concentration were established. A murine model was then developed with the transduced 4T1 cells for the ex vivo portion of the work. Non-transduced cells were implanted in a control group. Blood was drawn from mice in both groups over the course of 29 days. Antibody-conjugated nanoshells were incubated with the blood samples and detection of single CTCs was achieved in a dark field microscope. Low levels of nonspecific binding were observed in the control group for non-transduced cells and across different cell types normally found in peripheral blood (e.g. lymphocytes). All positive and negative subjects were successfully identified. Chapter 7 provides an outlook of the work presented here and elaborates on possible directions to further develop the use of nanoshells in bioapplications and spectroscopy. / Graduate / 2019-05-03

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This research investigates an extension of the glancing angle deposition (GLAD) technique and a biosensing application of films produced by GLAD. The extension to GLAD, called phi-sweep (PS), improves column isolation compared to films grown by traditional GLAD (TG) as well as modifies the column tilt angle, , of the slanted columns according to tan(_{PS}) = tan(_{TG}) cos(), where is the sweep angle. The biosensing application makes use of localized surface plasmon resonance in noble metal GLAD films functionalized with rabbit immunoglobulin G (rIgG) to detect binding of anti-rabbit immunoglobulin G (anti-rIgG) to the films' surface. The extinction peak red-shifts a distance dependent on the concentration of anti-rIgG solution in a manner described by the Langmuir isotherm with a saturation value, _{max}, of 29.4 0.7 nm and a surface confined thermodynamic binding constant, K, of (2.7 0.3)10 M. / Microsystems and Nanodevices

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.

Doctor of Philosophy / Department of Chemistry / Christine M. Aikens / Gold and silver particles with dimensions less than a nanometer possess unique characteristics and properties that are different from the properties of the bulk. They demonstrate a non–zero HOMO–LUMO gap that can reach up to 3.0 eV. These differences arise from size quantization effects in the metal core due to the small number of atoms. These nanoparticles have attracted great interest for decades both in fundamental and applied research. Small gold clusters protected by various types of ligands are of interest because ligands allow obtaining gold nanoclusters with given sizes, shapes and properties. Three main families of organic ligands are usually used for stabilization of gold nanoclusters: phosphine ligands, thiolate ligands and DNA. Usually, optical properties of these NPs are studied using optical absorption spectroscopy. Unfortunately, sometimes this type of spectrum is poorly resolved and tends to appear very similar for different complexes. In these cases, circular dichroism (CD) and magnetic circular dichroism (MCD) spectroscopy can be applied. However, the interpretation of experimental CD and MCD spectra is a complicated process. In this thesis, theoretically simulated CD and MCD spectra were combined with optical absorption spectra to study optical activity for octa– and nona– and undecanuclear gold clusters protected by mono– and bidentate phosphine ligands. Additionally, optical properties of bare and DNA protected silver NPs were studied. Theoretical CD spectra were examined to learn more about the origin of chirality in chiral organometallic complexes, and to contribute to the understanding of the difference in chiroptical activity of gold clusters stabilized by different phosphine ligands and DNA–stabilized silver clusters. Furthermore, optical properties of the small centered gold clusters Au₈(PPh₃)₈²⁺ and Au₉(PPh₃)₈³⁺ were examined by optical absorption and MCD spectra using TDDFT. Theoretical MCD spectra were also used to identify the plasmonic behavior of silver nanoparticles. These results showed that CD and MCD spectroscopy yield more detailed information about optical properties and electronic structure of the different chemical systems than optical absorption spectroscopy alone. Theoretical simulation of the CD and MCD spectra together with optical absorption spectra can be used to assist in the understanding of empirically measured CD and MCD and provide useful information about optical properties and electronic structure.

Different types of plasmonic nanostructures are proposed and examined experimentally and theoretically, with a view towards sensing applications. First, a self-assembly approach was developed to create arrays of well-ordered glass-supported gold nanoparticles (AuNPs) with controllable particle size and inter-particle spacing. Then, a periodic array of gold nano-disks (AuNDs) supported by a Bragg reflector was proposed and examined in a search for Fano resonances in its optical response. Arrays of heptamer-arranged nanoholes (HNH) in a thin gold film were also proposed and explored theoretically and experimentally, revealing a very rich spectrum of resonances, several exhibiting a Fano lineshape. A commercial implementation of the vectorial finite element method (FEM) was used to model our plasmonic structures. Taking advantage of the periodic nature of the structures, a unit cell containing a single element was modelled. The transmittance, reflectance or absorbance spectra were computed, and the associated electromagnetic fields were obtained by solving the vector wave equations for the electromagnetic field vectors throughout the structures, subject to the applicable boundary conditions, and the applied source fields. The sensing performance of the structures, based on the bulk sensitivity, surface sensitivity and figure of merit (FOM) was calculated. First, a novel bottom-up fabrication approach was applied (by our collaborators) to form a periodic array of AuNPs with controllable size over large areas on SiO2 substrates. In this method, self-assembly of block copolymer micelles loaded with metal precursors was combined with a seeding growth route to create ordered AuNPs of desired size. It was shown that this new fabrication method offers a new approach to tune the AuNP size and edge-to-edge inter-particle spacing while preserving the AuNP ordering. The optical characteristics of the AuNP arrays, such as their size, interparticle spacing, localized surface plasmon resonance (LSPR) wavelength, and bulk sensitivity, were examined, numerically and experimentally. This proposed novel fabrication method is applicable for low-cost mass-production of large-area arrays of high-quality AuNPs on a substrate for sensing applications. Then, we proposed and examined the formation of Fano resonances in a plasmonic-dielectric system consisting of uncoupled gold nano-disk (AuND) arrays on a quarter-wave dielectric stack. The mechanism behind the creation of Fano resonances was explained based on the coherent interference between the reflection of the Bragg stack and the LSPPs of the AuNDs. Fano parameters were obtained by fitting the computational data to the Fano formula. The bulk sensitivities and figure of merit of the Fano resonances were calculated. This plasmonic structure supports Fano resonances with a linewidth around 9 nm which is much narrower than the individual AuND LSPP bandwidth ( 80 nm) and the Bragg stack bandwidth ( 100 nm). Supporting Fano resonances with such a narrow linewidth, the structure has a great potential to be used for sensing applications. Also, this metallic-dielectric nanostructure requires no near-field coupling between AuNDs to generate the Fano resonances. So, the AuNDs can be located far enough from each other to simplify the potential fabrication process. The optical properties of HNH arrays on an SiO2 substrate were investigated, numerically and experimentally. Helium focused ion beam (HeFIB) milling was applied (by Dr. Choloong Hahn) to fabricate well-ordered and well-defined arrays of HNHs. Transmittance spectra of the structures were obtained as the optical response, which exhibits several Fano resonances. Then, the mechanism behind the formation of the Fano resonances was explained, and the sensing performance of the structure was inspected by measuring the bulk sensitivities. This array of nanohole cluster is exciting because it supports propagating SPPs and LSPPs, and also Wood’s anomaly waves, which makes the optical response very rich in excitations and spectral features. Also, as a periodic array of sub-wavelength metallic nanoholes, the system produces extraordinary optical transmission - highly enhanced transmission through (otherwise) opaque metallic films at specific wavelengths, facilitating measurement acquisition in transmission.

Influence optical response on underetching of plasmonic antennas is observed in this thesis. When light falls with resonant wavelength on the optical antennas, the electromagnetic field is amplified near this antennas. The resonant wavelength depends on the length of the antenna and on effective refractive index given by the ambient properties around the antenna. The contact surface with substrate (dielectric) is reduced by underetching the antenna and the effective refractive index is changed and thus the optical response of the antenna is changed.