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BiInO3 is a potentially polar oxide with distinct optical properties whose origin could result from a surface that has not been well characterized. The surface properties of BiInO3 thin films have been characterized here by temperature dependent angle-resolved x-ray photoemission spectroscopy. A large surface to bulk core-level binding energy shift for the In 3d5/2 core-level is identified, indicating a surface very different from the bulk. BiInO3 terminates in indium oxide and loses bismuth from the surface of the film at T = 573 K. The Debye–Waller plots suggest effective Debye temperatures of 263 ± 10 and 556 ± 27 K for the surface and bulk components of In 3d core-level, respectively.

We have performed depth profile studies of the structure of PbZr0.2Ti0.8O3 films of different thicknesses deposited on SrTiO3 substrates prepared by pulsed laser deposition, using grazing incident x-ray scattering (GIXS). The in-plane structure of the films reveals these consist of up to three domains, one c-axis domain, and two a-axis domains, denoted a1 and a2. GIXS measurements show the evolution of in-plane compression of the lattice parameter as a function of depth within the films, particularly in the a1 domains. This strain evolution is accompanied by the presence of twist grain boundaries in the plane in some films. The measured in-plane lattice parameters are asymmetric, which suggests an orthorhombic distortion of the lattice in the plane of the films.

Epitaxial ferroelectric films undergoing a cubic-tetragonal phase transformation relax internal stresses due to the structural phase transformation and the difference in the thermal expansion coefficients of the film and the substrate by forming polydomain structures. The most commonly observed polydomain structure is the c/a/c/a polytwin which only partially relieves the internal stresses. Relatively thicker films may completely reduce internal stresses if all three variants of the ferroelectric phase are brought together such that the film has the same in-plane size as the substrate. In this article, we provide experimental evidence on the formation of the three-domain structure based on transmission electron microscopy in 450 nm thick (001) PbZr0.2Ti0.8O3 films on (001) SrTiO3 grown by pulsed laser deposition. X-ray diffraction studies show that the film is fully relaxed. Experimental data is analyzed in terms of a domain stability map. It is shown that the observed structure in epitaxial ferroelectric...

We have studied the effect of misfit strain on the microstructure and properties of ferroelectric lead zirconate titanate thin films. We have changed the misfit strain by varying the film thickness and studied the thickness effect on the domain formation of epitaxial PbZr0.2Ti0.8O3 (PZT) films grown by pulsed laser deposition on (001) LaAlO3 substrates with La0.5Sr0.5CoO3 (LSCO) electrodes. The nominal thickness of the PZT films was varied from 60 to 400 nm with the LSCO electrode thickness kept constant at 50 nm. X-ray diffraction experiments show that the films relax via the formation of a domains, the fraction of which increase with the ferroelectric film thickness. The c-axis lattice constant of PZT films calculated from the 002 reflection decreases with increasing film thickness and approaches the bulk value of ∼0.413 nm in the films thicker than 300 nm. Cross-sectional transmission electron microscopy images reveal that the a-domain fraction and period increase with increasing film thickness. The relaxation of misfit strain in the film is accompanied by systematic changes in the polarization properties, as well as the switching fields, quantified by the coercive field and the activation field.

Solid state dewetting and the subsequent morphological changes for platinum thin films grown on zinc oxide (ZnO) buffered (001) silicon substrates (Pt/ZnO/SiO2/(001)Si system) is investigated under vacuum conditions via a custom-designed confocal laser microscope coupled with a laser heating system. Live imaging of thin film dewetting under a range of heating and quenching vacuum ambients reveals events including hillock formation, hole formation, and hole growth that lead to formation of a network of Pt ligaments, break up of Pt ligaments to individual islands and subsequent Pt islands shape reformation, in chronological fashion. These findings are corroborated by ex-situ materials characterization and quantitative electron microscopy analysis. A secondary hole formation via blistering before film rupture is revealed to be the critical stage, after which a rapid dewetting catastrophe occurs. This process is instantaneous and cannot be captured by ex-situ methods. Finally, an intermetallic phase forms at 900 °C and alters the morphology of Pt islands, suggesting a practical limit to the thermal environments that may be used for these platinized silicon wafers in vacuum conditions.

Domain microstructures in single crystal lamellae of 88%Pb(Zn1/3Nb2/3)O3-12%PbTiO3 (cut from bulk using focused ion beam milling) have been mapped using both piezoresponse force microscopy and transmission electron microscopy. Dramatic changes from mottled microstructures typical of relaxors to larger scale domains typical of ferroelectrics have been noted. Stresses associated with substrate clamping are suspected as the cause for the transition from short- to long-range polar order, akin to effects induced by cation ordering achieved by thermal quenching.

Cation intermixing at functional oxide interfaces remains a highly controversial area directly relevant to interface-driven nanoelectronic device properties. Here, we systematically explore the cation intermixing in epitaxial (001) oriented multiferroic bismuth ferrite (BFO) grown on a (001) lanthanum aluminate (LAO) substrate. Aberration corrected dedicated scanning transmission electron microscopy and electron energy loss spectroscopy reveal that the interface is not chemically sharp, but with an intermixing of ∼2 nm. The driving force for this process is identified as misfit-driven elastic strain. Landau-Ginzburg-Devonshire-based phenomenological theory was combined with the Sheldon and Shenoy formula in order to understand the influence of boundary conditions and depolarizing fields arising from misfit strain between the LAO substrate and BFO film. The theory predicts the presence of a strong potential gradient at the interface, which decays on moving into the bulk of the film. This potential gradient...

Trilayer heterostructures consisting of a ferroelectric bismuth ferrite (BFO) film sandwiched between ferromagnetic lanthanum strontium manganese oxide (LSMO) films were fabricated using pulsed laser deposition. Both BFO thicknesses (20 nm, 5 nm) and cooling rates were varied to investigate the role of processing parameters on the chemistry of the interfaces. The interfaces were investigated using a dedicated aberration corrected scanning transmission electron microscope (STEM) operated at 100 kV via STEM-high angle annular dark field (STEM-HAADF) and STEM-electron energy loss spectroscopy (STEM-EELS) modes. Combined analysis through STEM-HAADF and STEM-EELS revealed the formation of lattice distortion in certain regions of the BFO layer for the ∼5 nm film. Piezoresponse force microscopy (PFM) studies of the ∼5 nm BFO sample revealed weak ferroelectric domain switching. Stacking fault defects with mixed valence manganese (Mn-B site cation) were formed in the top LSMO layer when the heterostructure was coo...

Detailed structural investigations on the substitution-induced structural phase transition from the rhombohedral phase to an orthorhombic phase in (Bi,RE)FeO3 epitaxial thin films (RE = La, Sm, and Dy) grown on (100) SrTiO3 substrates are presented. X ray diffraction reveals that the unit cell dimensions of the orthorhombic phase are strongly dependent on the type of the RE dopant. For RE = La3+ ion, which has an ionic size comparable to the Bi3+ ion, the unit cell is found to be a0 × a0 × 2a0, where a0 is the pseudo-cubic lattice parameter. This is in contrast with the √2a0 × √2a0 × 2a0 unit cell for the case of smaller ionic radius RE (= Sm and Dy) elements. While clear double-hysteresis loops in the polarization versus electric-field curves due to field-induced transitions are observed for smaller ionic radius RE (= Sm and Dy), no signature of the double hysteresis loops is observed for the RE = La case across the structural boundary. We have also performed systematic tracking of the structural phases ...

We investigate the interfacial structure of PbZr0.20Ti0.80O3 (PZT)/La0.67Sr0.33MnO3 (LSMO)/SrTiO3 heterostructures by combining low-magnification transmission electron microscopy imaging and spectroscopy techniques with high-resolution spherical-aberration corrected scanning transmission electron microscopy imaging, geometrical phase analysis, and spectroscopy results. For certain thickness regimes, the interface between PZT and LSMO is found to have a significant density of planar defects at the interface. Both A-site cation (Pb) diffusivity and highly inhomogeneous local strains are observed at the boundaries of the defect areas. It is proposed that Pb is incorporated as PbO Ruddlesden–Popper planar fault within the LSMO. These results underline the importance of chemical fluctuations caused by long-range strain fields associated with defect cores.

We develop a nonlinear thermodynamic model to predict the phase stability of ultrathin epitaxial (001)-oriented ferroelectric PbZr1−xTixO3 (PZT) films with x=1.0, 0.9, 0.8, and 0.7 on substrates which induce anisotropic in-plane strains. The theoretical formalism incorporates the relaxation by misfit dislocations at the film deposition temperature, the possibility of formation of ferroelectric polydomain structures, and the effect of the internal electric field that is generated due to incomplete charge screening at the film-electrode interfaces and the termination of the ferroelectric layer. This analysis allows the development of misfit strain phase diagrams that provide the regions of stability of monodomain and polydomain structures at a given temperature, film thickness, and composition. It is shown that the range of stability for rotational monodomain phase is markedly increased in comparison to the same ferroelectric films on isotropic substrates. Furthermore, the model finds a strong similarity be...

We investigate theoretically ferroelastic domain fractions in a heteroepitaxial bilayer consisting of (001) tetragonal PbZrxTi1-xO3and (001) rhombohedral PbZrxTi1-xO3on a thick (001) passive substrate as a function of the lattice misfit strain between layers and the substrate. By considering the self-strain in each layer and the indirect elastic interaction between the layers, we provide a numerical analysis of the relative domain fractions in the tetragonal layer of a (001)PbZr0.2Ti0.8O3/ (001) PbZr0.8Ti0.2O3and (001)PbZr0.4Ti0.6O3/ (001) PbZr0.6Ti0.4O3bilayer structure as a function of the tetragonal layer thickness on (001) LaAlO3, (001) SrTiO3, and (001) MgO. It is found that the elastic coupling between the tetragonal and rhombohedral layers leads to an excess elastic energy in the tetragonal layer, resulting in a two to three times increase in the ferroelastic domain volume fraction of the tetragonal layer compared to single-layer films of similar thickness. These results show alternate ways of engineering ferroelastic domain structures in ferroelectric thin films. Refereed/Peer-reviewed

Landau–Devonshire-type phenomenological thermodynamic theory is employed to explain the electric field dependence of piezoelectric properties of tetragonal single domain PbZrxTi1−xO3 (PZT). The strong nonlinearity of the converse piezoelectric coefficient under a large external electric field is proved to be intrinsic both in bulk crystal and epitaxial tetragonal PZT thin films. The tunability of piezoelectric responses by an external electric field and its dependence on the film/substrate misfit and elastic compliance of thin films are characterized quantitatively. The theoretical predictions are in good agreement with the experimental results of piezoresponse scanning microscopy. Due to the large tunability of piezoresponse in it, PZT 50/50 (x=0.5) epitaxial film is a promising candidate for use in future tunable devices.