Brahlek Matthew, Stoica Vladimir A, Lapano Jason, Zhang Lei, Akamatsu Hirofumi, Tung I-Cheng, Gopalan Venkatraman, Walko Donald A, Wen Haidan, Freeland John W, Engel-Herbert Roman
Department of Materials Science and Engineering, Pennsylvania State University, University Park, Pennsylvania 16801, USA.
Advanced Photon Source, Argonne National Laboratory, Argonne, Illinois 60439, USA.
Struct Dyn. 2019 Jan 18;6(1):014502. doi: 10.1063/1.5045704. eCollection 2019 Jan.
Due to the strong dependence of electronic properties on the local bonding environment, a full characterization of the structural dynamics in ultrafast experiments is critical. Here, we report the dynamics and structural refinement at nanosecond time scales of a perovskite thin film by combining optical excitation with time-resolved X-ray diffraction. This is achieved by monitoring the temporal response of both integer and half-integer diffraction peaks of LaVO in response to an above-band-gap 800 nm pump pulse. We find that the lattice expands by 0.1% out of plane, and the relaxation is characterized by a biexponential decay with 2 and 12 ns time scales. We analyze the relative intensity change in half-integer peaks and show that the distortions to the substructure are small: the oxygen octahedral rotation angles decrease by ∼0.3° and La displacements decrease by ∼0.2 pm, which directly corresponds to an ∼0.8° increase in the V-O-V bond-angles, an in-plane V-O bond length reduction of ∼0.3 pm, and an unchanged out-of-plane bond length. This demonstration of tracking the atomic positions in a pump-probe experiment provides experimentally accessible values for structural and electronic tunability in this class of materials and will stimulate future experiments.
由于电子性质强烈依赖于局部键合环境,在超快实验中对结构动力学进行全面表征至关重要。在此,我们通过将光激发与时间分辨X射线衍射相结合,报告了钙钛矿薄膜在纳秒时间尺度上的动力学和结构细化情况。这是通过监测LaVO的整数和半整数衍射峰对高于带隙的800 nm泵浦脉冲的时间响应来实现的。我们发现晶格在面外方向膨胀了0.1%,弛豫过程表现为具有2 ns和12 ns时间尺度的双指数衰减。我们分析了半整数峰的相对强度变化,并表明子结构的畸变很小:氧八面体旋转角度减小了约0.3°,La位移减小了约0.2 pm,这直接对应于V - O - V键角增加了约0.8°,面内V - O键长度减少了约0.3 pm,面外键长度不变。在泵浦 - 探测实验中对原子位置的这种追踪证明为这类材料的结构和电子可调性提供了实验上可获取的值,并将推动未来的实验。