We studied the kinetics of the formation of iron oxide nanocrystals obtained from the solution-phase thermal decomposition of iron-oleate complex via the "heating-up" process. To obtain detailed information on the thermal decomposition process and the formation of iron oxide nanocrystals in the solution, we performed a thermogravimetric-mass spectrometric analysis (TG-MS) and in-situ magnetic measurements using SQUID. The TG-MS results showed that iron-oleate complex was decomposed at around 320 degrees C. The in-situ SQUID data revealed that the thermal decomposition of iron-oleate complex generates intermediate species, which seem to act as monomers for the iron oxide nanocrystals. Extensive studies on the nucleation and growth process using size exclusion chromatography, the crystallization yield data, and TEM showed that the sudden increase in the number concentration of the nanocrystals (burst of nucleation) is followed by the rapid narrowing of the size distribution (size focusing). We constructed a theoretical model to describe the "heating-up" process and performed a numerical simulation. The simulation results matched well with the experimental data, and furthermore they are well fitted to the well-known LaMer model that is characterized by the burst of nucleation and the separation of nucleation and growth under continuous monomer supply condition. Through this theoretical work, we showed that the "heating-up" and "hot injection" processes could be understood within the same theoretical framework in which they share the characteristics of nucleation and growth stages.
We have observed unusual ferromagnetic properties in single-crystalline CoSi nanowire ensemble, in marked contrast to the diamagnetic CoSi in bulk. High-density freestanding CoSi nanowires with B20 crystal structure are synthesized by a vapor-transport-based method. The reaction of cobalt chloride precursor with a Si substrate produces high-aspect-ratio CoSi nanowires. The high-resolution transmission electron microscopy and electron diffraction studies reveal superlattice structure in CoSi nanowires with twice the lattice parameter of simple cubic CoSi lattice. The zero-field-cooled and field-cooled (ZFC-FC) measurements from the nanowire ensemble show freezing of the disordered surface spins at low temperatures. The magnetoresistance (MR) measurements of single nanowire devices show a negative MR whose magnitude gets larger at lower temperatures.
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