Klebson L. Da Silva, Dirk Menzel, Armin Feldhoff, Christian Kübel, Michael Bruns, Andrea Paesano, Jr., Andre Düvel, Martin Wilkening, Mohammad Ghafari, Horst Hahn, Fred J. Litterst, Paul Heitjans, Klaus D. Becker e Vladimir  Sepelák

The Journal of Physical Chemistry C – Volume: 115; Pages: 7209–7217; DOI: dx.doi.org/10.1021/jp110128t; 2011

A one-step synthesis of nanostructured bismuth ferrite (BiFeO3) via mechanochemical processing of a α-Fe2O3/Bi2O3 mixture at room temperature is reported. The mechanically
induced phase evolution of the mixture is followed by XRD and 57Fe Mössbauer spectroscopy. It is shown that the mechanosynthesis of the rhombohedrally distorted perovskite BiFeO3 phase is completed after 12 h. Compared to the traditional synthesis route, the mechanochemical process used here represents a one-step, high-yield, low-temperature, and low-cost procedure for the synthesis of BiFeO3. High-resolution TEM and XRD studies reveal a nonuniform structure of mechanosynthesized BiFeO3 nanoparticles consisting of a crystalline core surrounded by an amorphous surface shell. The latter is found to exhibit an extra-ordinarily high metastability causing a rapid crystallization of nanoparticles under irradiation with electrons. In situ high-resolution TEM observations of the crystallization clearly show that the heterogeneous processes of nucleation and growth of bismuth iron oxide crystallites are spatially confined to the amorphous surface regions. This fact provides access to the elucidation of the mechanism of mechanosynthesis. It is demonstrated that the mechanosynthesized ferrite nanoparticles exhibit a partial super-paramagnetism at room temperature. Quantitative information on the short-range structure and hyperfine interactions, provided by the nuclear spectroscopic technique, is complemented by an investigation of the magnetic behavior of nanostructured BiFeO3 on a macroscopic scale by means of SQUID technique. As a consequence of canted spins in the surface shell of nanoparticles, the mechanosynthesized BiFeO3 exhibits an enhanced magnetization, an enhanced coercivity, and a shifted hysteresis loop.