J. Karthik

Ferroelectric polarization reversal via successive ferroelastic transitions

Switchable polarization makes ferroelectrics a critical component in memories, actuators and electro-optic devices, and potential candidates for nanoelectronics. Although many studies of ferroelectric switching have been undertaken, much remains to be understood about switching in complex domain structures and in devices. In this work, a combination of thin-film epitaxy, macro- and nanoscale property and switching characterization, and molecular dynamics simulations are used to elucidate the nature of switching in PbZr(0.2)Ti(0.8)O3 thin films. Differences are demonstrated between (001)-/(101)- and (111)-oriented films, with the latter exhibiting complex, nanotwinned ferroelectric domain structures with high densities of 90° domain walls and considerably broadened switching characteristics. Molecular dynamics simulations predict both 180° (for (001)-/(101)-oriented films) and 90° multi-step switching (for (111)-oriented films) and these processes are subsequently observed in stroboscopic piezoresponse force microscopy. These results have implications for our understanding of ferroelectric switching and offer opportunities to change domain reversal speed.

Temperature and thickness evolution and epitaxial breakdown in highly strained BiFeO3 thin films

Author(s): Damodaran, AR; Lee, S; Karthik, J; MacLaren, S; Martin, LW | Abstract: We present the temperature- and thickness-dependent structural and morphological evolution of strain-induced transformations in highly strained epitaxial BiFeO 3 films deposited on LaAlO 3 (001) substrates. Using high-resolution x-ray diffraction and temperature-dependent scanning-probe-based studies, we observe a complex temperature- and thickness-dependent evolution of phases in this system. A thickness-dependent transformation from a single, monoclinically distorted, tetragonal-like phase to a complex mixed-phase structure in films with thicknesses up to ∼200 nm is the consequence of a strain-induced spinodal instability in the BiFeO 3/LaAlO 3 system. Additionally, a breakdown of this strain-stabilized metastable mixed-phase structure to nonepitaxial microcrystallites of the parent rhombohedral structure of BiFeO 3 is observed to occur at a critical thickness of ∼300 nm. We further propose a mechanism for this abrupt breakdown that provides insight into the competing nature of the phases in this system.

Epitaxial Ferroelectric Heterostructures Fabricated by Selective Area Epitaxy of SrRuO3 Using an MgO Mask

Illustration of a new high-temperature hard-mask process based on traditional lithography and selective wet-etching of MgO. The hard mask is compatible with standard nano-lithography techniques and heat treatments in excess of 1000 °C. Here, this technique is applied to produce temperature-stable contacts that give rise to low leakage, improved fatigue properties, and excellent high-temperature stability in ferroelectric thin-film capacitors.

Effect of domain walls on the electrocaloric properties of Pb(Zr1−x,Tix)O3 thin films

The electrocaloric properties of polydomain epitaxial Pb(Zr1-x,Tix)O3 thin films are investigated using a Ginzburg-Landau-Devonshire thermodynamic model as a function of strain, temperature, and composition for 0.65 ≤ x ≤ 1. Polarization transitions driven by epitaxial strain and extrinsic contributions from domain wall displacements are found to dramatically impact the electrocaloric response. Careful choice of epitaxial misfit strain and composition allows one to harness the intrinsic and extrinsic contributions to obtain large adiabatic temperature changes much below the Curie temperature of the material.

Stationary domain wall contribution to enhanced ferroelectric susceptibility

In ferroelectrics, the effect of domain wall motion on properties has been widely studied, but non-motional or stationary contributions from the volume of material within the domain wall itself has received less attention. Here we report the measurement of stationary domain wall contributions to permittivity in PbZr(0.2)Ti(0.8)O₃ films. Studies of (001)-, (101)- and (111)-oriented epitaxial films reveal that (111)-oriented films, in which the motional domain wall contributions are frozen out, exhibit permittivity values approximately three times larger than the intrinsic response alone. This discrepancy can only be accounted for by considering a stationary contribution from the domain wall volume of the material that is 6-78 times larger than the bulk response, and is consistent with predictions of the enhancement of susceptibilities within 90° domain walls. This work offers new insights into the microscopic origin of dielectric enhancement and provides a pathway to engineer the dielectric response of materials.

Thickness-dependent crossover from charge- to strain-mediated magnetoelectric coupling in ferromagnetic/piezoelectric oxide heterostructures.

Magnetoelectric oxide heterostructures are proposed active layers for spintronic memory and logic devices, where information is conveyed through spin transport in the solid state. Incomplete theories of the coupling between local strain, charge, and magnetic order have limited their deployment into new information and communication technologies. In this study, we report direct, local measurements of strain- and charge-mediated magnetization changes in the La0.7Sr0.3MnO3/PbZr0.2Ti0.8O3 system using spatially resolved characterization techniques in both real and reciprocal space. Polarized neutron reflectometry reveals a graded magnetization that results from both local structural distortions and interfacial screening of bound surface charge from the adjacent ferroelectric. Density functional theory calculations support the experimental observation that strain locally suppresses the magnetization through a change in the Mn-eg orbital polarization. We suggest that this local coupling and magnetization suppression may be tuned by controlling the manganite and ferroelectric layer thicknesses, with direct implications for device applications.

Polarization screening-induced magnetic phase gradients at complex oxide interfaces

Thin-film oxide heterostructures show great potential for use in spintronic memories, where electronic charge and spin are coupled to transport information. Here we use a La0.7Sr0.3MnO3 (LSMO)/PbZr0.2Ti0.8O3 (PZT) model system to explore how local variations in electronic and magnetic phases mediate this coupling. We present direct, local measurements of valence, ferroelectric polarization and magnetization, from which we map the phases at the LSMO/PZT interface. We combine these experimental results with electronic structure calculations to elucidate the microscopic interactions governing the interfacial response of this system. We observe a magnetic asymmetry at the LSMO/PZT interface that depends on the local PZT polarization and gives rise to gradients in local magnetic moments; this is associated with a metal-insulator transition at the interface, which results in significantly different charge-transfer screening lengths. This study establishes a framework to understand the fundamental asymmetries of magnetoelectric coupling in oxide heterostructures.

Direct observation of ferroelectric domain switching in varying electric field regimes using in situ TEM

In situ Transmission Electron Microscopy (TEM) techniques can potentially fill in gaps in the current understanding interfacial phenomena in complex oxides. Select multiferroic oxide materials, such as BiFeO(3) (BFO), exhibit ferroelectric and magnetic order, and the two order parameters are coupled through a quantum-mechanical exchange interaction. The magneto-electric coupling in BFO allows control of the ferroelectric and magnetic domain structures via applied electric fields. Because of these unique properties, BFO and other magneto-electric multiferroics constitute a promising class of materials for incorporation into devices such as high-density ferroelectric and magnetoresistive memories, spin valves, and magnetic field sensors. The magneto-electric coupling in BFO is mediated by volatile ferroelastically switched domains that make it difficult to incorporate this material into devices. To facilitate device integration, an understanding of the microstructural factors that affect ferroelastic relaxation and ferroelectric domain switching must be developed. In this article, a method of viewing ferroelectric (and ferroelastic) domain dynamics using in situ biasing in TEM is presented. The evolution of ferroelastically switched ferroelectric domains in BFO thin films during many switching cycles is investigated. Evidence of partial domain nucleation, propagation, and switching even at applied electric fields below the estimated coercive field is revealed. Our observations indicate that the occurrence of ferroelastic relaxation in switched domains and the stability of these domains is influenced the applied field as well as the BFO microstructure. These biasing experiments provide a real time view of the complex dynamics of domain switching and complement scanning probe techniques. Quantitative information about domain switching under bias in ferroelectric and multiferroic materials can be extracted from in situ TEM to provide a predictive tool for future device development.

Pyroelectric current measurements on PbZr0.2Ti0.8O3 epitaxial layers

We report pyroelectric current measurements on 150 nm thick PbZr0.2Ti0.8O3 (PZT) epitaxial films using frequency-domain thermal measurements over the range 0.02 Hz–1.3 MHz. The measured pyroelectric currents are proportional to the rate of temperature change, from ∼10−5 A/m2 to ∼103 A/m2 over the range 10−2 to 106 K/s. The film temperature oscillation is controlled using either a hotplate, microfabricated heater, or modulated laser, and the pyroelectric current is measured from a microelectrode fabricated onto the film. The measured pyroelectric coefficient of the PZT films is nearly constant across the entire frequency range at ≈−200 μC/m2K.

High-temperature piezoresponse force microscopy

We report high temperature piezoresponse force microscopy (PFM) on 100 nm thick PbZr0.2Ti0.8O3 films fabricated on a miniature heater stage. The microfabricated resistive heater allows local temperature control up to 1000 °C with minimal electrostatic interactions. The PFM measurements were used to collect piezoelectric hysteresis loops over the temperature range 25–400 °C. The piezoresponse increases with temperature and then decreases rapidly near 400 °C, which is indicative of ferroelectric-paraelectric phase transition.