Diffraction studies for stoichiometry effects in BaTiO3 grown by molecular beam epitaxy on Ge(001)

Abstract

In this work, we present a systematic study of the effect of the stoichiometry of BaTiO3 (BTO) films grown on the Ge(001) substrate by molecular-beam-epitaxy using different characterization methods relying on beam diffraction, including reflection high-energy electron diffraction (RHEED), X-ray diffraction (XRD), and selected-area electron diffraction in transmission electron microscopy. Surprisingly, over a wide range of [Ba]/[Ti] ratios, as measured by the Rutherford backscattering spectrometry, all the BTO layers exhibit the same epitaxial relationship 〈100〉BTO(001)//〈110〉Ge(001) with the substrate, describing a 45° lattice rotation of the BTO lattice with respect to the Ge lattice. However, varying the [Ba]/[Ti] ratio does change the diffraction behavior. From RHEED patterns, we can derive that excessive [Ba] and [Ti] generate twinning planes and a rougher surface in the non-stoichiometric BTO layers. XRD allows us to follow the evolution of the lattice constants as a function of the [Ba]/[Ti] ratio, providing an option for tuning the tetragonality of the BTO layer. In addition, we found that the intensity ratio of the 3 lowest-order Bragg peaks I(001)/I(002), I(101)/I(002), and I(111)/I(002) derived from ω − 2θ scans characteristically depend on the BTO stoichiometry. To explain the relation between observed diffraction patterns and the stoichiometry of the BTO films, we propose a model based on diffraction theory explaining how excess [Ba] or [Ti] in the layer influences the diffraction response.