NORTHWESTERN UNIVERSITY Nanoscale Investigation of Platinum Nanoparticles on SrTiO3 Grown via Physical Vapor Deposition and Atomic Layer Deposition A DISSERTATION SUBMITTED TO THE GRADUATE SCHOOL IN PARTIAL FULFILMENT OF THE REQUIREMENTS for the degree DOCTOR OF PHILOSOPHY

This dissertation examines growth of platinum nanoparticles from vapor deposition on SrTiO 3 using a characterization approach that combines imaging techniques and X-ray methods. The primary suite of characterization probes includes atomic force microscopy (AFM), grazing-incidence small-angle X-ray scattering (GISAXS), X-ray fluorescence (XRF), scanning electron microscopy (SEM), and X-ray absorption spectroscopy (XAS). The vapor deposition techniques include physical vapor deposition (PVD) by evaporation and atomic layer deposition (ALD). For the PVD platinum study, AFM/XRF showed ~10 nm nanoparticles separated by an average of 100 nm. The combination of AFM, GISAXS, and XRF indicated that the nanoparticles observed with AFM were actually comprised of closely spaced, smaller nanoparticles. These conclusions were supported by high-resolution SEM. The unusual behavior of platinum nanoparticles to aggregate without coalescence or sintering was observed previously by other researchers using transmissision electron microscopy (TEM). Platinum nanoparticle growth was also investigated on SrTiO 3 (001) single crystals using ALD to nucleate nanoparticles that subsequently grew and coalesced into granular films as the ALD progresses. The expected growth rate for the early stages of ALD showed a twofold increase which was attributed to the platinum deposition occurring faster on the bare substrate. Once the nanoparticles had coalesced into a film, steady state ALD growth proceeded. The formation of nanoparticles was attributed to the atomic diffusion of platinum atoms on iv the surface in addition to direct growth from the ALD precursor gases. The platinum ALD nanoparticles were also studied on SrTiO 3 nanocube powders. The SrTiO 3 nanocubes average 60 nm on a side and the cube faces have a {001} orientation. The ALD proceeded in a similar fashion as on the single crystal substrates where the deposition rate was twice as fast as the steady state growth rate. The Pt nanoparticle size increased linearly starting at ~0.7 nm for 1 ALD cycle to ~3 nm for 5 ALD cycles. The platinum chemical state was also investigated using X-ray absorption spectroscopy. Platinum nanoparticles ~1 nm or smaller tended to be oxidized. For larger nanoparticles, the platinum state systematically approached that of bulk platinum metal as the size (number of ALD cycles) increased. The platinum loading was exceptionally low, ~ 10-3 mg cm-2. v ACKNOWLEDGEMENT The counsel to " do something difficult for my posterity " was once given to me. This work would not have been possible without the help from many collaborators, friends, and loved ones. I will …