ABSTRACT
In this work, we investigated the MOCVD conditions to synthesize thin films with the hexagonal P63cm h-LuMnO3 phase as a potential low-band gap ferroelectric material. The main parameters investigated were the ratio of organometallic starting materials, substrate temperature, and annealing effect. Two different substrates were used in the study: fused silica (SiO2) glass and platinized silicon (Pt\Ti\SiO2\Si(100)). In order to investigate the thermodynamic stability and quality of the developed phases, a detailed analysis of the crystal structure, microstructure, morphology, and roughness of the films was performed by X-ray diffractometer, scanning electron microscopy (SEM), energy dispersive spectrometry (EDS), Raman spectroscopy, and piezoelectric force microscopy (PFM). Molar compositions in the film within 0.93 < |Lu|/|Mn| < 1.33 were found to be suitable for obtaining a single-phase h-LuMnO3. The best films were obtained by depositions at 700 °C, followed by thermal treatments at 800 °C for long periods of up to 12 h. These films exhibited a highly crystalline hexagonal single phase with a relatively narrow direct band gap, around 1.5 eV, which is within the expected values for the h-LuMnO3 system.
ABSTRACT
Zirconia- and hafnia-based thin films have attracted tremendous attention in the past decade because of their unexpected ferroelectric behavior at the nanoscale, which enables the downscaling of ferroelectric devices. The present work reports an unprecedented ferroelectric rhombohedral phase of ZrO2 that can be achieved in thin films grown directly on (111)-Nb:SrTiO3 substrates by ion-beam sputtering. Structural and ferroelectric characterizations reveal (111)-oriented ZrO2 films under epitaxial compressive strain exhibiting switchable ferroelectric polarization of about 20.2 µC/cm2 with a coercive field of 1.5 MV/cm. Moreover, the time-dependent polarization reversal characteristics of Nb:SrTiO3/ZrO2/Au film capacitors exhibit typical bell-shaped curve features associated with the ferroelectric domain reversal and agree well with the nucleation limited switching (NLS) model. The polarization-electric field hysteresis loops point to an activation field comparable to the coercive field. Interestingly, the studied films show ferroelectric behavior per se, without the need to apply the wake-up cycle found in the orthorhombic phase of ZrO2. Overall, the rhombohedral ferroelectric ZrO2 films present technological advantages over the previously studied zirconia- and hafnia-based thin films and may be attractive for nanoscale ferroelectric devices.
ABSTRACT
Perovskite-type manganites, such as Pr1-xCaxMnO3, La1-xCaxMnO3 and La1-xSrxMnO3 solid solutions, are set forth as a case study of ferroelectricity formation mechanisms associated with the appearance of site- and bond-centered orbital ordering which breaks structural inversion symmetry. Even though the observation of macroscopic ferroelectricity may be hindered by the finite conductivity of manganites, polarization can still exist in nanoscale volumes. We use Piezoresponse Force Microscopy to probe local bias induced modifications of electrical and electromechanical properties at the manganite surface. Clear bias-induced piezocontrast and local hysteresis loops are observed for La0.89Sr0.11MnO3 and Pr0.60Ca0.40MnO3 compounds providing convincing evidence of the existence of locally induced polar states well above the transition temperature of the CO phase, while the reference samples without CO behavior show no ferroelectric-like response. Such coexistence of ferroelectricity and magnetism in manganites due to the charge ordering (CO) under locally applied electric field opens up a new pathway to expand the phase diagrams of such systems and to achieve spatially localized multiferroic effects with a potential to be used in a new generation of memory cells and data processing circuits.
