Y. L. Tang

Atomic-scale mapping of dipole frustration at 90 degrees charged domain walls in ferroelectric PbTiO3 films

The atomic-scale structural and electric parameters of the 90° domain-walls in tetragonal ferroelectrics are of technological importance for exploring the ferroelectric switching behaviors and various domain-wall-related novel functions. We have grown epitaxial PbTiO3/SrTiO3 multilayer films in which the electric dipoles at 90° domain-walls of ferroelectric PbTiO3 are characterized by means of aberration-corrected scanning transmission electron microscopy. Besides the well-accepted head-to-tail 90° uncharged domain-walls, we have identified not only head-to-head positively charged but also tail-to-tail negatively charged domain-walls. The widths, polarization distributions, and strains across these charged domain-walls are mapped quantitatively at atomic scale, where remarkable difference between these domain-walls is presented. This study is expected to provide fundamental information for understanding numerous novel domain-wall phenomena in ferroelectrics.

Atomic mapping of Ruddlesden-Popper faults in transparent conducting BaSnO3-based thin films

Doped BaSnO3 has arisen many interests recently as one of the promising transparent conducting oxides for future applications. Understanding the microstructural characteristics are crucial for the exploration of relevant devices. In this paper, we investigated the microstructural features of 0.001% La doped BaSnO3 thin film using both conventional and aberration corrected transmission electron microscopes. Contrast analysis shows high densities of Ruddlesden-Popper faults in the film, which are on {100} planes with translational displacements of 1/2a < 111 > . Atomic EELS element mappings reveal that the Ruddlesden-Popper faults are Ba-O layer terminated, and two kinds of kink structures at the Ruddlesden-Popper faults with different element distributions are also demonstrated. Quantitative analysis on lattice distortions of the Ruddlesden-Popper faults illustrates that the local lattice spacing poses a huge increment of 36%, indicating that large strains exist around the Ruddlesden-Popper faults in the film.

On the benefit of aberration-corrected HAADF-STEM for strain determination and its application to tailoring ferroelectric domain patterns.

Revealing strains on the unit-cell level is essential for understanding the particular performance of materials. Large-scale strain variations with a unit-cell resolution are important for studying ferroelectric materials since the spontaneous polarizations of such materials are strongly coupled with strains. Aberration-corrected high-angle-annular-dark-field scanning transmission electron microscopy (AC-HAADF-STEM) is not so sensitive to the sample thickness and therefore thickness gradients. Consequently it is extremely useful for large-scale strain determination, which can be readily extracted by geometrical phase analysis (GPA). Such a combination has various advantages: it is straightforward, accurate on the unit-cell scale, relatively insensitive to crystal orientation and therefore helpful for large-scale. We take a tetragonal ferroelectric PbTiO3 film as an example in which large-scale strains are determined. Furthermore, based on the specific relationship between lattice rotation and spontaneous polarization (Ps) at 180° domain-walls, the Ps directions are identified, which makes the investigation of ferroelectric domain structures accurate and straightforward. This method is proposed to be suitable for investigating strain-related phenomena in other ferroelectric materials.

Giant linear strain gradient with extremely low elastic energy in a perovskite nanostructure array

Although elastic strains, particularly inhomogeneous strains, are able to tune, enhance or create novel properties of some nanoscale functional materials, potential devices dominated by inhomogeneous strains have not been achieved so far. Here we report a fabrication of inhomogeneous strains with a linear gradient as giant as 106 per metre, featuring an extremely lower elastic energy cost compared with a uniformly strained state. The present strain gradient, resulting from the disclinations in the BiFeO3 nanostructures array grown on LaAlO3 substrates via a high deposition flux, induces a polarization of several microcoulomb per square centimetre. It leads to a large built-in electric field of several megavoltage per metre, and gives rise to a large enhancement of solar absorption. Our results indicate that it is possible to build up large-scale strain-dominated nanostructures with exotic properties, which in turn could be useful in the development of novel devices for electromechanical and photoelectric applications.

Local Enhancement of Polarization at PbTiO3/BiFeO3 Interfaces Mediated by Charge Transfer

Ferroelectrics hold promise for sensors, transducers, and telecommunications. With the demand of electronic devices scaling down, they take the form of nanoscale films. However, the polarizations in ultrathin ferroelectric films are usually reduced dramatically due to the depolarization field caused by incomplete charge screening at interfaces, hampering the integrations of ferroelectrics into electric devices. Here, we design and fabricate a ferroelectric/multiferroic PbTiO3/BiFeO3 system, which exhibits discontinuities in both chemical valence and ferroelectric polarization across the interface. Aberration-corrected scanning transmission electron microscopic study reveals an 8% elongation of out-of-plane lattice spacing associated with 104%, 107%, and 39% increments of δTi, δO1, and δO2 in the PbTiO3 layer near the head-to-tail polarized interface, suggesting an over ∼70% enhancement of polarization compared with that of bulk PbTiO3. Besides that in PbTiO3, polarization in the BiFeO3 is also remarkably enhanced. Electron energy loss spectrum and X-ray photoelectron spectroscopy investigations demonstrate the oxygen vacancy accumulation as well as the transfer of Fe3+ to Fe2+ at the interface. On the basis of the polar catastrophe model, FeO2/PbO interface is determined. First-principles calculation manifests that the oxygen vacancy at the interface plays a predominate role in inducing the local polarization enhancement. We propose a charge transfer mechanism that leads to the remarkable polarization increment at the PbTiO3/BiFeO3 interface. This study may facilitate the development of nanoscale ferroelectric devices by tailing the coupling of charge and lattice in oxide heteroepitaxy.

Origin of the Bloch-type polarization components at the 180° domain walls in ferroelectric PbTiO3

Determination of atomic and electronic structures of ferroelectric domain walls is crucial to understand and explore their unusual properties. Using first-principles calculations based on the density functional theory, we explored the atomic and electronic structures of 180° domain walls in PbTiO3, in order to understand the origin of Bloch-type polarization components. It is found that Bloch-type polarization components originate from the large displacements of Pb atoms and the Pb-O hybridization at the domain walls. The development of Bloch-type polarization components significantly reduce the domain wall energies and change the Peierls barriers of domain wall motion in different orientations.

Large scale arrays of four-state vortex domains in BiFeO3 thin film

Exotic domain states, like vortex, offer the promise of superior properties and the potential disclination strain is a key factor for their formation in ferroelectrics. Here we show that large scale arrays of four-state vortex domains can be obtained in rhombohedral BiFeO3 thin films grown on PrScO3 substrates by pulsed laser deposition. Cs-corrected scanning transmission electron microscopy demonstrates that each vortex domain is comprised of four ferroelectric variants with two 180° domain walls and two 109° domain walls. Atomic mappings of the lattice distortions unit cell by unit cell reveal that the cores of the vortex might be charged. The strains are mainly concentrated on domain walls. The formation mechanism of such large scale vortex-like states was discussed.

Giant Polarization Sustainability in Ultrathin Ferroelectric Films Stabilized by Charge Transfer

Ferroelectricity is generally deteriorated or even vanishes when the ferroelectric films are downsized to unit cell scale. To maintain and enhance the polarization in nanoscale ferroelectrics are of scientific and technological importance. Here, giant polarization sustainability is reported in a series of ultrathin PbTiO3 films scaled down to three unit cells grown on NdGaO3 (110) substrates with La0.7 Sr0.3 MnO3 as bottom electrodes. Atomic mappings via aberration-corrected scanning transmission electron microscopy demonstrate the robust ferroelectricity for the sub-10 nm thick film. For the 1.2 nm thick film, the polarization reaches ≈50 µC cm-2 . The 2 nm thick film possesses a polarization as high as the bulk value. The films ranging from 10 to 35 nm display a giant elongation of out-of-plane lattice parameter, which corresponds to a polarization of 100 µC cm-2 , 20% larger than that of the bulk PbTiO3 . The giant enhancement of polarization in the present films is proposed to result from the charge transfer at the La0.7 Sr0.3 MnO3 /PbTiO3 interface, as supported by the anomalous decrease of Mn valence measured from X-ray photoelectron spectroscopy. These results reveal the significant role of charge transfer at interfaces in improving large polarizations in ultrathin ferroelectrics and are meaningful for the development of future electronic devices.

Controlled Growth and Atomic-Scale Mapping of Charged Heterointerfaces in PbTiO3/BiFeO3 Bilayers

Functional oxide interfaces have received a great deal of attention owing to their intriguing physical properties induced by the interplay of lattice, orbital, charge, and spin degrees of freedom. Atomic-scale precision growth of the oxide interface opens new corridors to manipulate the correlated features in nanoelectronics devices. Here, we demonstrate that both head-to-head positively charged and tail-to-tail negatively charged BiFeO3/PbTiO3 (BFO/PTO) heterointerfaces were successfully fabricated by designing the BFO/PTO film system deliberately. Aberration-corrected scanning transmission electron microscopic mapping reveals a head-to-head polarization configuration present at the BFO/PTO interface, when the film was deposited directly on a SrTiO3 (001) substrate. The interfacial atomic structure is reconstructed, and the interfacial width is determined to be 5-6 unit cells. The polarization on both sides of the interface is remarkably enhanced. Atomic-scale structural and chemical element analyses exhibit that the reconstructed interface is rich in oxygen, which effectively compensates for the positive bound charges at the head-to-head polarized BFO/PTO interface. In contrast to the head-to-head polarization configuration, the tail-to-tail BFO/PTO interface exhibits a perfect coherency, when SrRuO3 was introduced as a buffer layer on the substrates prior to the film growth. The width of this tail-to-tail interface is estimated to be 3-4 unit cells, and oxygen vacancies are supposed to screen the negative polarization bound charge. The formation mechanism of these distinct interfaces was discussed from the perspective of charge redistribution.

Misfit Strain Relaxation of Ferroelectric PbTiO3/LaAlO3 (111) Thin Film System.

Ferroelectric thin films grown on high index substrates show unusual structural and switching dynamics due to their special strain states. Understanding the misfit relaxation behavior is crucial to facilitate the high index thin film growth with improved quality. In this paper, ferroelectric PbTiO3 thin films were grown on LaAlO3 (111) substrates by pulsed laser deposition technique. The microstructures were investigated by combinations of conventional and aberration-corrected transmission electron microscopy. Diffraction contrast analysis and high resolution imaging reveal that high density interfacial dislocations were distributed at the interfaces. These dislocations have mixed character with Burgers vectors of a <110> and line directions of <112>. The edge components of the dislocations, with the Burgers vectors parallel to the interface, accommodate the lattice mismatch and are the main contributor to the misfit relaxation of this system. The formation mechanism of these dislocations is proposed and discussed to elucidate the novel mismatch relaxation behavior of <111> oriented perovskite films.