Strategy to control magnetic coercivity by elucidating crystallization pathway-dependent microstructural evolution of magnetite mesocrystals.

Mesocrystals are assemblies of smaller crystallites and have attracted attention because of their nonclassical crystallization pathway and emerging collective functionalities. Understanding the mesocrystal crystallization mechanism in chemical routes is essential for precise control of size and microstructure, which influence the function of mesocrystals. However, microstructure evolution from the nucleus stage through various crystallization pathways remains unclear. We propose a unified model on the basis of the observation of two crystallization pathways, with different ferric (oxyhydr)oxide polymorphs appearing as intermediates, producing microstructures of magnetite mesocrystal via different mechanisms. An understanding of the crystallization mechanism enables independent chemical control of the mesocrystal diameter and crystallite size, as manifested by a series of magnetic coercivity measurements. We successfully implement an experimental model system that exhibits a universal crystallite size effect on the magnetic coercivity of mesocrystals. These findings provide a general approach to controlling the microstructure through crystallization pathway selection, thus providing a strategy for controlling magnetic coercivity in magnetite systems.

Surface-Mediated Solidification of a Semiconducting Polymer during Time-Controlled Spin-Coating.

Spin-casting a polymer semiconductor solution over a short period of only a few seconds dramatically improved the molecular ordering and charge transport properties of the resulting semiconductor thin films. In this process, it was quite important to halt spinning before the drying line propagation had begun. Here, we elucidated the effects of the substrate surface characteristics on the drying kinetics during spin-coating, systematically investigated the microstructural evolution during semiconducting polymer solidification, and evaluated the performances of the resulting polymer field-effect transistors. We demonstrated that the spin time required to enhance the molecular ordering and electrical properties of the polythiophene thin films was strongly correlated with the solidification onset time, which was altered by surface treatments introduced onto the substrate surfaces.

Understanding Solidification of Polythiophene Thin Films during Spin-Coating: Effects of Spin-Coating Time and Processing Additives.

Spin-coating has been used extensively in the fabrication of electronic devices; however, the effects of the processing parameters have not been fully explored. Here, we systematically characterize the effects of the spin-coating time on the microstructure evolution during semiconducting polymer solidification in an effort to establish the relationship between this parameter and the performances of the resulting polymer field-effect transistors (FETs). We found that a short spin-coating time of a few seconds dramatically improve the morphology and molecular order in a conjugated polymer thin film because the π-π stacking structures formed by the polymer molecules grow slowly and with a greater degree of order due to the residual solvent present in the wet film. The improved ordering is correlated with improved charge carrier transport in the FETs prepared from these films. We also demonstrated the effects of various processing additives on the resulting FET characteristics as well as on the film drying behavior during spin-coating. The physical properties of the additives are found to affect the film drying process and the resulting device performance.