Manipulating the Ferroelectric Domain States and Structural Distortion in Epitaxial BiFeO3 Ultrathin Films via Bi Nonstoichiometry.

Exploring and manipulating domain configurations in ferroelectric thin films are of critical importance for the design and fabrication of ferroelectric heterostructures with a novel functional performance. In this study, BiFeO3 (BFO) ultrathin films with various Bi/Fe ratios from excess Bi to deficient Bi have been grown on (La0.7Sr0.3)MnO3 (LSMO)-covered SrTiO3 substrates by a laser molecular beam epitaxy system. Atomic force microscopy and piezoresponse force microscopy measurements show that both the surface morphology and ferroelectric polarization of the films are relevant to Bi nonstoichiometry. More significantly, a Bi-excess thin film shows an upward (from substrate to film surface) uniform ferroelectric polarization, whereas a Bi-deficient thin film exhibits a downward uniform polarization, which means the as-grown polarization of BFO thin films can be controlled by changing the Bi contents. Atomic-scale structural and chemical characterizations and second-harmonic generation measurements reveal that two different kinds of structural distortions and interface atomic configurations in the BFO/LSMO heterostructures can be induced by the change of Bi nonstoichiometry, leading to the two opposite as-grown ferroelectric polarizations. It has also been revealed that the band gap of BFO thin films can be modulated via Bi nonstoichiometry. These results demonstrate that Bi nonstoichiometry plays a key role on the ferroelectric domain states and physical properties of BFO thin films and also open a new avenue to manipulate the structure and ferroelectric domain states in BFO thin films.

Controllable growth of ultrathin BiFeO3 from finger-like nanostripes to atomically flat films.

BiFeO3 (BFO) ultrathin films with nominal thicknesses from 2 to 12 nm were grown with a SrRuO3 (SRO) buffer layer on TiO2-terminated (001) SrTiO3 (STO) substrates using pulsed laser deposition. The surface morphologies and domain configurations of the thin films were investigated using atomic force microscopy and piezoelectric force microscopy. Periodical one-dimensional finger-like nanostripes of BFO on the SRO covered STO substrates were observed. With increasing thickness, the BFO ultrathin films develop from the finger-like nanostripes to an atomically flat surface. The formation of the finger-like nanostructures of BFO is related to the atomic step or terrace structure of the substrate. The BFO nanostripes and the atomically flat thin films both show good ferroelectricity. The as-grown domain orientations of the BFO ultrathin films are ascribed to the chemical terminations at the surface of the SRO layer. These results indicate that the surface morphologies and the domain configurations of BFO ultrathin films can be artificially designed by using substrates with optimized terrace structures and chemical termination, and these films are potentially useful in multifunctional nanoelectronic devices.