Phase transformation at controlled locations in nanowires by in situ electron irradiation

Solid state phase transformations have drawn great attention because they can be effectively exploited to control the microstructure and property of materials. Understanding the physics of such phase transformation processes is critical to designing materials with controlled structure and with desired properties. However, in traditional ex situ experiments, it is hard to achieve position controlled phase transformations or obtain desirable crystal phase on nanometer scale. Meanwhile the underlying mechanisms of the reaction processes are not fully understood due to the lack of direct and real-time observation. In this paper, we observe phase transformation from body-centered tetragonal PX-PbTiO₃ to monoclinic TiO₂(B) on the atomic scale by in situ electron irradiation during heat treatment in transmission electron microscope, at pre-defined locations on the sample. We demonstrate that by controlling the location of the incident electron beam, a porous TiO₂(B) crystal structure can be formed at the desired area on the nanowire, which is difficult to achieve by traditional synthesis methods. Upon in situ heating, the Pb atoms in the crystal migrate out of the pristine nanowire through inelastic scattering under incident electrons while high temperature(> 400 °C) provides energy for the crystallization of TiO₂(B) and the volatilization of a substantial number of Pb atoms, which makes the resultingTiO₂(B) nanowires to be porous. In contrast, at temperatures < 400 °C, the segregated Pb atoms form Pb particles and the TiO_x nanowires remain in the amorphous state. This work not only provides in situ visualization of the phase transition from the PX-PbTiO₃ to monoclinic TiO₂(B), but also suggests a crystallography engineering strategy to obtain the desired crystal phase at controlled locations on the nanometer scale.