Functionalization and Characterization of Gold Nanoparticles

Surface characterization of gold nanoparticles (AuNPs) is necessary to obtain a thorough understanding of the AuNP properties and ultimately realize their full potential in applications. The work described in this dissertation strives to the structure and composition of AuNPs using highly surface sensitive techniques such as X-ray photoelectron spectroscopy (XPS) and time-of-flight secondary ion mass spectrometry (ToF-SIMS) in addition to the more widely used characterization techniques such as transmission electron microscopy (TEM), fourier transform infrared spectroscopy (FTIR) and UV-VIS spectroscopy.;Self-assembled monolayers (SAMs) of alkanethiols were used to modify AuNPs surfaces to create positively and negatively charged surfaces. Functionalization with carboxylic acid terminated alkanethiol SAMs (COON-SAMs) was first optimized to produce clean and stable negatively charged AuNPs. Using 14nm and 40nm diameter AuNPs in combination with C11 and C16 chain length COOH-SAMs, it was found that addition of NH4OH during functionalization coupled with dialysis purification produced AuNPs that did not aggregate and did not have unbound thiols. Effects of AuNP size and COOH-SAM chain lengths were studied using 14, 25 and 40nm average diameter AuNPs functionalized with C6, C8, C11 and C16 COOH-SAMs. Flat Au surfaces were also functionalized with the COOH-SAMs for comparison. It was shown that the 14nm AuNPs with C16 COOH-SAMs were the most stable and had crystalline-like, well-ordered SAM structures. The SAMs on the 40nm AuNPs had similar surface chemistry as the SAMs on the flat Au surfaces. The effective photoelectron take-off angle of the C16 COOH-SAM decreased when the size of the AuNP increased. It was also shown that when using Kratos AxisUltra DLD XPS instrument in the hybrid mode, it was important to consider effects of both the hybrid mode and the AuNPs curvature when calculating overlayer thickness of the SAMs on AuNPs. Using the Kratos in the electrostatic mode, the overlayer thickness of C16 COON-SAM was 21A on a flat Au surface, which was comparable with previously reported values. However, the apparent thickness of the same SAM on the 14nm AuNPs was 31A, indicating the curvature of the AuNPs had an effect on the XPS measurements. To produce the positively charged AuNP surfaces, amine terminated alkanethiols (NH2 -thiols) with a C2 chain length were used in one-step AuNP synthesis and functionalization process followed by a ligand-exchange reaction with C11 chain length NH2-thiols. It was found that 14 days were needed for the ligand-exchange to be complete. After the ligand-exchange, it was found that the AuNPs with C11 NH2-SAMs were stable and could be purified, unlike AuNPs with C2 NH2-SAMs which aggregated upon purification. The C11 NH2-SAMs had both unbound and oxidized sulfur, which could be removed/converted after hydrochloric acid treatment.;SESSA (simulation of electron spectra for surface analysis) allowed better interpretation of the XPS data of SAMs on AuNPs and flat Au. Comparing SESSA and experimental XPS data, it was found that C16 COON-SAM on a flat Au surface was 20A thick with a 1.5A hydrocarbon contamination overlayer and 1.05 relative surface roughness. After geometric weighing of angle-resolved XPS and SESSA data, it was found that C16 COOH-SAMs on 14nm AuNPs were 17A thick with a 1.5A hydrocarbon contamination. The decreased SAM thickness on the AuNPs is likely due to an increased tilt angle of the alkane chains or increased disorder in the SAM.