Christopher R. Winkler

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.

Accessing intermediate ferroelectric switching regimes with time-resolved transmission electron microscopy

BiFeO3 (BFO) is one of the most widely studied magneto-electric multiferroics. The magneto-electric coupling in BiFeO3, which allows for the control of the ferroelectric and magnetic domain structures via applied electric fields, can be used to incorporate BiFeO3 into novel spintronics devices and sensors. Before BiFeO3 can be integrated into such devices, however, a better understanding of the dynamics of ferroelectric switching, particularly in the vicinity of extended defects, is needed. We use in situ transmission electron microscopy (TEM) to investigate the response of ferroelectric domains within BiFeO3 thin films to applied electric fields at high temporal and spatial resolution. This technique is well suited to imaging the observed intermediate ferroelectric switching regimes, which occur on a time- and length-scale that are too fine to study via conventional scanning-probe techniques. Additionally, the spatial resolution of transmission electron microscopy allows for the direct study of the dynam...

LaAlO 3 /SrTiO 3 Epitaxial Heterostructures by Atomic Layer Deposition

Thin films of LaAlO3 were deposited on TiO2-terminated (100) SrTiO3 crystals by atomic layer deposition (ALD), using tris(iso-propylcyclopentadienyl)lanthanum and trimethyl aluminum precursors. Water was used as the oxidizer. The film composition was shown to be controlled by the ratio of La/Al precursor pulses during ALD, with near-stoichiometric LaAlO3 resulting at precursor pulse ratios of 4/1 to 5/1. Films near the stoichiometric LaAlO3 composition were shown to crystallize on subsequent annealing to form epitaxial LaAlO3/SrTiO3 heterostructures. Electrical characterization of these structures was done by two-terminal direct-current (DC) current–voltage scans at room temperature and under high-vacuum conditions. The results show electrical conductivity for the ALD-deposited epitaxial LaAlO3/SrTiO3 heterostructures, which turns on for thickness above four unit cells for the LaAlO3 film.

Real-Time Observation of Local Strain Effects on Nonvolatile Ferroelectric Memory Storage Mechanisms

We use in situ transmission electron microscopy to directly observe, at high temporal and spatial resolution, the interaction of ferroelectric domains and dislocation networks within BiFeO3 thin films. The experimental observations are compared with a phase field model constructed to simulate the dynamics of domains in the presence of dislocations and their resulting strain fields. We demonstrate that a global network of misfit dislocations at the film-substrate interface can act as nucleation sites and slow down domain propagation in the vicinity of the dislocations. Networks of individual threading dislocations emanating from the film-electrode interface play a more dramatic role in pinning domain motion. These dislocations may be responsible for the domain behavior in ferroelectric thin-film devices deviating from conventional Kolmogorov-Avrami-Ishibashi dynamics toward a Nucleation Limited Switching model.

Epitaxial strain and its relaxation at the LaAlO3/SrTiO3 interface

A series of LaAlO3 thin films with different thicknesses were deposited by pulsed laser deposition at temperatures from 720 °C to 800 °C. The results from grazing incidence x-ray diffraction and reciprocal space mapping indicate that a thin layer of LaAlO3 adjacent to the SrTiO3 substrate remains almost coherently strained to the substrate, while the top layer starts to relax quickly above a certain critical thickness, followed by a gradual relaxation at larger film thickness when they are grown at lower temperatures. The atomic force microscopy results show that the fast relaxation is accompanied by the formation of cracks on the film surface. This can be ascribed to the larger energy release rate when compared with the resistance of LaAlO3 to cracking, according to calculations from the Griffith fracture theory. For films grown at 720 °C, a drop in sheet resistance by two orders of magnitude is observed when the top layer starts to relax, indicating a relationship between the strain and the conductivity of the two-dimensional electron gas at the LaAlO3/SrTiO3 interface. The strain engineered by growth temperature provides a useful tool for the manipulation of the electronic properties of oxide heterointerfaces.

Asymmetric Response of Ferroelastic Domain-Wall Motion under Applied Bias.

The switching of domains in ferroelectric and multiferroic materials plays a central role in their application to next-generation computer systems, sensing applications, and memory storage. A detailed understanding of the response to electric fields and the switching behavior in the presence of complex domain structures and extrinsic effects (e.g., defects and dislocations) is crucial for the design of improved ferroelectrics. In this work, in situ transmission electron microscopy is coupled with atomistic molecular dynamics simulations to explore the response of 71° ferroelastic domain walls in BiFeO3 with various orientations under applied electric-field excitation. We observe that 71° domain walls can have intrinsically asymmetric responses to opposing biases. In particular, when the electric field has a component normal to the domain wall, forward and backward domain-wall velocities can be dramatically different for equal and opposite fields. Additionally, the presence of defects and dislocations can strongly affect the local switching behaviors through pinning or nucleation of the domain walls. These results offer insight for controlled ferroelastic domain manipulation via electric-field engineering.