This thesis describes the synthesis of nanoparticles in the cores of spherical micelles
of poly(styrene)-b-poly(2-vinylpyridine) (PS-b-P2VP) and the subsequent deposition
of these nanoparticle loaded micelles onto substrates, generating self-assembled
nanomaterials with precisely-tuned regularly-spaced nanoparticles. Combining this
bottom-up method of nanopatterning with top-down lithographic techniques allowed
for the production of more complex surface patterns.
Specifically, nanoparticles of Au, ZnS and Ag2S were synthesized. The formation
mechanism of ZnS and Au nanoparticles were investigated using small angle X-ray
scattering (SAXS). Single gold nanoparticles with diameters ranging from 4–12 nm
were produced in the P2VP cores, with the size of the particles directly related to
the ionic loading of the micelles. ZnS nanoparticles synthesized using this method
had a unique hybrid substructure, consisting of small crystallites of ZnS embedded
in an amorphous matrix composed of ZnS and the core-forming polymer. The size
of the ZnS nanoparticles was dependent on the size of the ion-loaded core prior to
sulfidation. The synthesis method was developed further by synthesizing multiple
Ag2S particles in the micelle cores, that grew over time.
Surface deposition of ZnS nanoparticle loaded micelles and subsequent exposure
to hydrogen plasma and UV/ozone in order to remove the polymer shell resulted
in the formation of ZnS nanoarrays on silicon and glass substrates, whose interparticle
spacing could be directly controlled by varying the deposition protocol.
The functionalization of these nanopatterned surfaces was successfully achieved via
the attachment of poly-histidine tagged ICAM-1/CD54 to the nanoparticles surface.
The capability of producing micropatterns of the ZnS nanoparticles was demonstrated
by applying photolithography and focused ion beam lithography to surface
deposited nanoparticle loaded micelles. In this way, it was possible to create regions
of the substrate with or without ZnS nanoparticles.