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.
We demonstrate optical modes in InGaAs/GaAs microtubes acting as optical ring resonators. Self-supporting microtubes were fabricated by optical lithography and wet-etching processes utilizing the self-rolling mechanism of strained bilayers. The optical modes were probed by the photoluminescence of InAs quantum dots embedded in the tube's wall. In this novel microtube ring resonator we find a spectrum of sharp modes. They are in very good agreement with the theoretical results for a closed thin dielectric waveguide.
The optical properties of nanocrystals are drastically changed by the interaction with adjacent metal nanoparticles. By time-resolved photoluminescence spectroscopy, we investigate CdSe multishell nanocrystals coupled to self-assembled films of Au nanoparticles. The distance between emitter and metal is adjusted by coating the nanocrystals with silica shells. These NCs showed increased fluorescence intensity, a decreased fluorescence lifetime, strong blinking suppression, and fluorescence from gray states. These observations can be explained by the metal particle induced change of excitation and recombination rates.
We demonstrate the self-assembled creation of a novel type of strain-free semiconductor quantum dot (QD) by local droplet etching (LDE) with Al to form nanoholes in AlGaAs or AlAs surfaces and subsequent filling with GaAs. Since the holes are filled with a precisely defined filling level, we achieve ultrauniform LDE QD ensembles with extremely narrow photoluminescence (PL) linewidth of less than 10 meV. The PL peaks agree with a slightly anisotropic parabolic potential. Small QDs reveal indications for transitions between electron and hole states with different quantization numbers. For large QDs, a very small fine-structure splitting is observed.
We demonstrate the light-induced, reversible wettability of homogeneous nanocrystal-based, thin-film coatings composed of closely packed arrays of surfactant-capped anatase TiO 2 nanorods laterally oriented on various substrates. Under selective pulsed UV laser excitation, the oxide films exhibit a surface transition from a highly hydrophobic and superoleophilic state (water and oil contact angles of ∼110°and less than ∼8°, respectively) to a highly amphiphilic condition (water and oil contact angles of ∼20°and ∼3°, respectively). A mechanism is identified according to which the UV-induced hydrophilicity correlates with a progressive increase in the degree of surface hydroxylation of TiO 2 . The observed wettability changes are not accompanied by any noticeable photocatalytic degradation of the surfactants on the nanorods, which has been explained by the combined effects of the intense and pulsed irradiation regime and of the rodlike nanocrystal morphology. The organic ligands on the oxide are instead assumed to rearrange conformationally in response to the lightdriven surface reconstruction. The amphiphilic state of the UV-irradiated TiO 2 films is then considered as the macroscopic wetting result of alternating hydrophilic and oleophilic surface domains of nanoscale extension. Upon prolonged storage in the dark, ambient oxygen removes the newly implanted hydroxyl groups from the TiO 2 surfaces and consequently affects again the conformations of ligands such that the films are allowed to recover their native hydrophobic/superoleophilic properties.
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