Photochemical Synthesis of Silver Nanodecahedrons and Related Nanostructures for Plasmonic Field Enhancement Applications

Noble-metal nanocrystals have received considerable attention in recent years for their size and shape dependent localized surface Plasmon resonances (LSPR). Various applications based on colloidal nanoparticles, such as surface enhanced Raman scattering (SERS), surface enhanced fluorescence (SEF), plasmonic sensing, photothermal therapy etc., have been broadly explored in the field of biomedicine, because of their extremely large optical scattering and absorption cross sections, as well as giant electric field enhancement on their surface. However, despite its high chemical stability, gold exhibits quite large losses and electric field enhancement is comparatively weaker than silver. Silver nanoparticles synthesized by the traditional technique only cover an LSPR ranged from 420~500 nm. On the other hand, the range of 500~660 nm, which is covered by several easily available commercial laser lines, very limited colloidal silver nanostructures with controllable size and shape have been reported, and realization of tuning the resonance to longer wavelengths is very important for the practical applications. In this thesis, a systematic study on photochemical synthesis of silver nanodecahedrons (NDs) and related nanostructures, and their plasmonic field enhancements are presented.;First, the roles of chemicals and the light source during the formation of silver nanoparticles have been studied. We have also developed a preparation route for the production size-controlled silver nanodecahedrons (LSPR range 420 ~ 660 nm) in high purity. Indeed our experiments indicate that both the chemicals and the light sources can affect the shape and purity of final products. Adjusting the molar ratio between sodium citrate and silver nitrate can help to control the crystal structure following rapid reduction from sodium borohydride. Light from a blue LED (465 nm) can efficiently transform the polyvinylpyrrolidone stabilized small silver nanoparticles into silver NDs through photo excitation. These silver NDs acting as seeds can be re-grown into larger silver NDs with LSPR ranging from 490 nm to 590 nm, upon receiving LED irradiation with emission close to the LSPR of silver ND seeds, which are suspended in a precursor solution containing small silver nanoparticles. With the aid of centrifugation, silver NDs with high purity can be obtained. Furthermore, silver ND with a broad tuning range (LSPR 490 ~ 660 nm) can be synthesized from these seeds using irradiation from a 500 nm LED.;Second, the optical properties of silver NDs and their SERS application for sensitive molecular detection are presented. Raman signal obtained from silver NDs show remarkable advantage over noble nanoparticles of other shaped, thus revealing their strong localized field enhancement. Experimental results demonstrate that average enhancement factor from individual silver ND may be as high as 106. In order to explore their application for biosensing and bioimaging, stable silica coated SERS tags based on silver ND producing high Raman intensity have been studied. Our experiment results indicate that 10-8 M 4-MBA in solution can be detected by silver NDs modified silicon chip through SERS. Simulation result on the geometry of silver ND/silica spacer/gold film/substrate shows that the Raman sensitivity of the NDs modified chip can be further improved with the insertion of a dielectric/conductor film between them.;Finally, we present a photochemical method for the preparation of silver nanostructures preparation with the use of 633 nm laser. Silver nanostructures composed of silver nanoplates could be grown from small silver nanoparticles deposited on a glass substrate. The periodicity of the silver nanostructures is several micrometers, revealing that this photochemical method has the potential for “writing” silver pattern on a solid substrate. Raman spectroscopy has also been explored for real-time monitoring of silver nanostructure growth and SERS hotspots formation.