Relationships Between Processing, Structure And Properties Of Nanocrystal Quantum Dots And Superlattices
Nanocrystal quantum dots are novel materials of great scientific and technological interests. The attractive features of quantum dots include size-tunable optoelectronic properties, high optical absorption cross section and ease of synthesis and deposition. These unique features qualify quantum dots as a promising material platform for emerging technological applications such as photovoltaic devices, sensors, light emitting diodes and bioimaging. In most of the proposed applications, individual quantum dots cannot be utilized until they form macroscopic assemblies. Under proper conditions quantum dots self-assemble into periodical superlattices. The properties and performance of quantum dot assemblies depend on not only the intrinsic properties of isolated dots but also their spatial arrangement or ordering. Consequently the relationships between processing, structure and properties of quantum dots and superlattices are of great importance in guiding the design and fabrication of novel nanomaterials with advantageous features using quantum as building blocks. In this dissertation, I present my graduate research studying such trilateral relationships in lead chalcogenide quantum dot systems. The first half of this dissertation discusses the relationship between processing and structure of self-assembled superlattices. An overview of how the ligand-ligand interaction as the major driving force along with factors including particle size, shape, ligand morphology, solvents and interfaces determine superlattice morphology is provided and followed by specific examples. (1) By tuning surface ligand morphology of PbS quantum dots and growth conditions, the effective particles shape was altered and therefore different symmetries (fcc, bcc and bct) of superlattice were achieved. (2) The translational and orientational orderings in an fcc superlattice of cuboctahedron PbS quantum dots was decoded by small and wide angle x-ray scatterings. The dots showed two distinct orientations as a result of the interplay between particle shape and ligand attractions. (3) Study of the nucleation, orientational alignment and symmetry transformations of PbS nanocubes at solvent-air and solvent-substrate interfaces is presented to demonstrate the role of interfaces as templates in guiding superlattice formation. Presented in the second half of this dissertation are my research works using high pressure, which efficiently tunes both superlattice and atomic structures without altering chemistry, to probe the relationships between structure and properties of quantum dots systems. (1) Difference in the pressure-induced atomic phase transition pressure indicated that dots in bcc superlattice are more mechanically stable than those in fcc due to translational and orientational orderings. (2) Elastic stiffness of PbS quantum dots were found to show size-dependence which is explained by a core-shell model. (3) Size-dependent variation of band gap of PbS quantum dot under elevated pressure was observed and correlated to changes of atomic structure. (4) Quantum dots were innovatively used as a nano-scaled tool to uniaxially compress organic molecule chains and measure the force-length relationship of single molecules.
Clancy,Paulette; Thompson,Michael Olgar
Ph. D., Chemical Engineering
Doctor of Philosophy
dissertation or thesis