Confined-but-connected quantum solids via controlled ligand displacement.

Confined-but-connected quantum dot solids (QDS) combine the advantages of tunable, quantum-confined energy levels with efficient charge transport through enhanced electronic interdot coupling. We report the fabrication of QDS by treating self-assembled films of colloidal PbSe quantum dots with polar nonsolvents. Treatment with dimethylformamide balances the rates of self-assembly and ligand displacement to yield confined-but-connected QDS structures with cubic ordering and quasi-epitaxial interdot connections through facets of neighboring dots. The QDS structure was analyzed by a combination of transmission electron microscopy and wide-angle and small-angle X-ray scattering. Excitonic absorption signatures in optical spectroscopy confirm that quantum confinement is preserved. Transport measurements show significantly enhanced conductivity in treated films.

Interface-induced nucleation, orientational alignment and symmetry transformations in nanocube superlattices.

The self-assembly of colloidal nanocrystals into ordered superstructures depends critically on the shape of the nanocrystal building blocks. We investigated the self-assembly of cubic PbSe nanocrystals from colloidal suspensions in real-time using in situ synchrotron-based X-ray scattering. We combined small-angle and wide-angle scattering to investigate the translational ordering of nanocrystals and their orientational ordering in the lattice sites, respectively. We found that cubic PbSe nanocrystals assembled into a face-up (i.e., [100] normal to the interface) configuration at the liquid/substrate interface whereas nanocubes at the liquid/air interface assume a corner-up (i.e., [111] normal to the interface) configuration. The latter nanocrystal superlattice displays polymorphism as a function inter-NC separation distance. We explain the observed superlattice structure polymorphs in terms of the interactions directing the self-assembly. Insights into the directed self-assembly of superlattices gained from this study have important implication on the future development of nanocrystals as building blocks in artificial solids.

SnSe nanocrystals: synthesis, structure, optical properties, and surface chemistry.

The colloidal synthesis of SnSe nanoparticles is accomplished through the injection of bis[bis(trimethylsilyl)amino]tin(II) into hot trioctylphosphine:selenium in the presence of oleylamine. Through the manipulation of reaction temperature particles are grown with the average diameter reliably tuned to 4-10 nm. Quantum confinement is examined by establishing a relationship between particle size and band gap while the in depth growth dynamics are illuminated through UV-vis-NIR spectroscopy. Surface chemistry effects are explored, including the demonstration of useful ligand exchanges and the development of routes toward anisotropic particle growth. Finally, transient current-voltage properties of SnSe nanocrystal films in the dark and light are examined.

Nanoparticle metamorphosis: an in situ high-temperature transmission electron microscopy study of the structural evolution of heterogeneous Au:Fe2O3 nanoparticles.

High-temperature in situ electron microscopy and X-ray diffraction have revealed that Au and Fe2O3 particles fuse in a fluid fashion at temperatures far below their size-reduced melting points. With increasing temperature, the fused particles undergo a sequence of complex structural transformations from surface alloy to phase segregated and ultimately core-shell structures. The combination of in situ electron microscopy and spectroscopy provides insights into fundamental thermodynamic and kinetic aspects governing the formation of heterogeneous nanostructures. The observed structural transformations present an interesting analogy to thin film growth on the curved surface of a nanoparticle. Using single-particle observations, we constructed a phase diagram illustrating the complex relationships among composition, morphology, temperature, and particle size.

Timing matters: the underappreciated role of temperature ramp rate for shape control and reproducibility of quantum dot synthesis.

Understanding the coupled kinetic and thermodynamics factors governing colloidal nanocrystals nucleation and growth are critical factors in the predictable and reproducible synthesis of advanced nanomaterials. We show that the temporal temperature profile is decisive in tuning the particle shape from pseudo-spherical to monodisperse cubes. The shape of the nanocrystals was characterized by transmission electron microscopy and X-ray diffraction. We introduce a mechanism for the shape controlled synthesis in the context of temperature-dependent nucleation and growth and provide experimental evidence to support it.

Predicting nanocrystal shape through consideration of surface-ligand interactions.

Density functional calculations for the binding energy of oleic acid-based ligands on Pb-rich {100} and {111} facets of PbSe nanocrystals determine the surface energies as a function of ligand coverage. Oleic acid is expected to bind to the nanocrystal surface in the form of lead oleate. The Wulff construction predicts the thermodynamic equilibrium shape of the PbSe nanocrystals. The equilibrium shape is a function of the ligand surface coverage, which can be controlled by changing the concentration of oleic acid during synthesis. The different binding energy of the ligand on the {100} and {111} facets results in different equilibrium ligand coverages on the facets, and a transition in the equilibrium shape from octahedral to cubic is predicted when increasing the ligand concentration during synthesis.

Pulsed laser annealing of thin films of self-assembled nanocrystals.

We investigated how pulsed laser annealing can be applied to process thin films of colloidal nanocrystals (NCs) into interconnected nanostructures. We illustrate the relationship between incident laser fluence and changes in morphology of PbSe NC films relative to bulk-like PbSe films. We found that laser pulse fluences in the range of 30 to 200 mJ/cm(2) create a processing window of opportunity where the NC film morphology goes through interesting transformations without large-scale coalescence of the NCs. NC coalescence can be mitigated by depositing a thin film of amorphous silicon (a-Si) on the NC film. Remarkably, pulsed laser annealing of the a-Si/PbSe NC films crystallized the silicon while NC morphology and translational order of the NC film are preserved.