In the realm of semiconductor nanomaterials, a crystal lattice heavily doped with cation/anion vacancies or ionized atomic impurities is considered to be a general prerequisite to accommodating excess free carriers that can support localized surface plasmon resonance (LSPR). Here, we demonstrate a surfactant-assisted nonaqueous route to anisotropic copper sulfide nanocrystals, selectively trapped in the covellite phase, which can exhibit intense, size-tunable LSPR at near-infrared wavelengths despite their stoichiometric, undoped structure. Experimental extinction spectra are satisfactorily reproduced by theoretical calculations performed by the discrete dipole approximation method within the framework of the Drude-Sommerfeld model. The LSPR response of the nanocrystals and its geometry dependence are interpreted as arising from the inherent metallic-like character of covellite, allowed by a significant density of lattice-constitutional valence-band free holes. As a consequence of the unique electronic properties of the nanocrystals and of their monodispersity, coherent excitation of symmetric radial breathing modes is observed for the first time in transient absorption experiments at LSPR wavelengths.

A surfactant-assisted nonaqueous strategy, relying on high-temperature aminolysis of titanium carboxylate complexes, has been developed to access anisotropically shaped TiO2 nanocrystals selectively trapped in the metastable brookite phase. Judicious temporal manipulation of precursor supply to the reaction mixture enables systematic tuning of the nanostructure geometric features over an exceptionally wide dimensional range (30-200 nm). Such degree of control is rationalized within the frame of a self-regulated phase-changing seed-catalyzed mechanism, in which homogeneous nucleation, on one side, and heterogeneous nucleation/growth processes, on the other side, are properly balanced while switching from the anatase to the brookite structures, respectively, in a continuous unidirectional crystal development regime. The time variation of the chemical potential for the monomer species in the solution, the size dependence of thermodynamic structural stability of the involved titania polymorphs, and the reduced activation barrier for brookite nucleation onto initially formed anatase seeds play decisive roles in the crystal-phase- and shape-tailored growth of titania nanostructures by the present approach.

Colloidal semiconductor-magnetic hybrid nanocrystals with topologically controlled composition are fabricated by heterogeneous nucleation of spherical epsilon-Co domains onto anatase TiO2 nanorods. The latter can be selectively decorated at either their tips or at multiple locations along their longitudinal sidewalls, forming lattice-matched heterointerfaces regardless of the metal deposition sites. The possibility of switching between either heterostructure growth modes arises from the facet-dependent chemical reactivity of the oxide seeds, which is governed mainly by selective adhesion of the surfactants rather than by small differences in misfit-induced interfacial strain at the relevant junction points.

Asymmetric binary nanocrystals (BNCs), comprising one c-axis elongated anatase TiO2 section and one gamma-Fe2O3 spherical domain attached together, are synthesized by heterogeneous nucleation of iron oxide onto the longitudinal facets of TiO2 nanorods in a ternary surfactant mixture. The topologically controlled composition of the BNCs is ascertained by a combination of powder X-ray diffraction, Raman and Mössbauer spectroscopy, high-angle annular dark-field imaging, and high-resolution transmission electron microscopy lattice fringe mapping, while their size-dependent magnetic behavior is demonstrated by ac susceptibility measurements. The heteroepitaxial growth proceeds through a mechanism never observed before for colloidal nanoheterostructures: the two domains share a restricted and locally curved junction region, which accommodates efficiently the interfacial strain and retards the formation of misfit dislocations. It is believed that these BNCs, which combine the properties of two technologically relevant oxide materials, can pave the way to reinforced applications in several fields of nanoscience, such as in photocatalysis, in malignant cell treatments, and in nanocrystal assembly.