Controlled creation and displacement of charged domain walls in ferroelectric thin films.

Charged domain walls in ferroelectric materials are of high interest due to their potential use in nanoelectronic devices. While previous approaches have utilized complex scanning probe techniques or frustrative poling here we show the creation of charged domain walls in ferroelectric thin films during simple polarization switching using either a conductive probe tip or patterned top electrodes. We demonstrate that ferroelectric switching is accompanied - without exception - by the appearance of charged domain walls and that these walls can be displaced and erased reliably. We ascertain from a combination of scanning probe microscopy, transmission electron microscopy and phase field simulations that creation of charged domain walls is a by-product of, and as such is always coupled to, ferroelectric switching. This is due to the (110) orientation of the tetragonal (Pb,Sr)TiO3 thin films and the crucial role played by the limited conduction of the LSMO bottom electrode layer used in this study. This work highlights that charged domain walls, far from being exotic, unstable structures, as might have been assumed previously, can be robust, stable easily-controlled features in ferroelectric thin films.

Velocity Control of 180° Domain Walls in Ferroelectric Thin Films by Electrode Modification.

The velocity of individual 180° domain walls in thin ferroelectric films of PbZr0.1Ti0.9O3 is strongly dependent on the thickness of the top Pt electrode made by electron-beam induced deposition (EBID). We show that when the thickness is varied in the range <100 nm the domain wall velocity is seen to change by 7 orders of magnitude. We attribute this huge range of velocities to the similarly large range of resistivities for the EBID Pt electrode as extrapolated from four-point probe measurements. The domain wall motion is governed by the supply of charges to the domain wall, determined by the top electrode resistivity, and which is described using a modified Stefan Problem model. This has significant implications for the feasibility of ferroelectric domain wall nanoelectronics, wherein the speed of operation will be limited by the maximum velocity of the propagating domain wall front. Furthermore, by introducing sections of either modified thickness or width along the length of a "line" electrode, the domain wall velocity can be changed at these locations, opening up possibilities for dynamic regimes.

The variation of PbTiO3 bandgap at ferroelectric phase transition.

Optical properties of the PbTiO3 thin films fabricated by chemical solution deposition have been measured with variable angle spectroscopic ellipsometry in the spectral range of 1-6 eV and in the temperature interval from room temperature to 950 K. The optical response functions and band gap energy were determined in the whole temperature range. The direct band gap varies from the value 3.88 eV at room temperature to the value 3.67 eV just above the phase transition. The temperature dependence of the film lattice parameters was also measured by x-ray and it shows a strong correlation with the band gap. The comparison of experimental data with ab initio electronic structure calculations simulating the temperature development of dielectric function and band gap is also presented.

Controlling domain wall motion in ferroelectric thin films.

Domain walls in ferroic materials have attracted significant interest in recent years, in particular because of the unique properties that can be found in their vicinity. However, to fully harness their potential as nanoscale functional entities, it is essential to achieve reliable and precise control of their nucleation, location, number and velocity. Here, using piezoresponse force microscopy, we show the control and manipulation of domain walls in ferroelectric thin films of Pb(Zr,Ti)O3 with Pt top electrodes. This high-level control presents an excellent opportunity to demonstrate the versatility and flexibility of ferroelectric domain walls. Their position can be controlled by the tuning of voltage pulses, and multiple domain walls can be nucleated and handled in a reproducible fashion. The system is accurately described by analogy to the classical Stefan problem, which has been used previously to describe many diverse systems and is here applied to electric circuits. This study is a step towards the realization of domain wall nanoelectronics utilizing ferroelectric thin films.

Elastic coupling between nonferroelastic domain walls.

We reveal a strong elastic interaction between nonferroelastic domain walls in ferroelectric thin films. This interaction, having no analogue in bulk materials, is governed by elastic fields that are associated with the domain walls and extends to distances comparable to the film thickness. Such elastic widening of the nonferroelastic domain walls is shown to be particularly strong in common ferroelectric perovskites. The results are especially relevant for the control of domain wall propagation and the understanding of polarization dynamics.

The origin of antiferroelectricity in PbZrO3.

Antiferroelectrics are essential ingredients for the widely applied piezoelectric and ferroelectric materials: the most common ferroelectric, lead zirconate titanate is an alloy of the ferroelectric lead titanate and the antiferroelectric lead zirconate. Antiferroelectrics themselves are useful in large digital displacement transducers and energy-storage capacitors. Despite their technological importance, the reason why materials become antiferroelectric has remained allusive since their first discovery. Here we report the results of a study on the lattice dynamics of the antiferroelectric lead zirconate using inelastic and diffuse X-ray scattering techniques and the Brillouin light scattering. The analysis of the results reveals that the antiferroelectric state is a 'missed' incommensurate phase, and that the paraelectric to antiferroelectric phase transition is driven by the softening of a single lattice mode via flexoelectric coupling. These findings resolve the mystery of the origin of antiferroelectricity in lead zirconate and suggest an approach to the treatment of complex phase transitions in ferroics.

Ferroelectric polymer gates for non-volatile field effect control of ferromagnetism in (Ga, Mn)As layers.

(Ga, Mn)As and other diluted magnetic semiconductors (DMS) attract a great deal of attention for potential spintronic applications because of the possibility of controlling the magnetic properties via electrical gating. Integration of a ferroelectric gate on the DMS channel adds to the system a non-volatile memory functionality and permits nanopatterning via the polarization domain engineering. This topical review is focused on the multiferroic system, where the ferromagnetism in the (Ga, Mn)As DMS channel is controlled by the non-volatile field effect of the spontaneous polarization. Use of ferroelectric polymer gates in such heterostructures offers a viable alternative to the traditional oxide ferroelectrics generally incompatible with DMS. Here we review the proof-of-concept experiments demonstrating the ferroelectric control of ferromagnetism, analyze the performance issues of the ferroelectric gates and discuss prospects for further development of the ferroelectric/DMS heterostructures toward the multiferroic field effect transistor.

Low-symmetry phases in ferroelectric nanowires.

Ferroelectric nanostructures have recently attracted much attention due to the quest of miniaturizing devices and discovering novel phenomena. In particular, studies conducted on two-dimensional and zero-dimensional ferroelectrics have revealed original properties and their dependences on mechanical and electrical boundary conditions. Meanwhile, researches aimed at discovering and understanding properties of one-dimensional ferroelectric nanostructures are scarce. The determination of the structural phase and of the direction of the polarization in one-dimensional ferroelectrics is of technological importance, since, e.g., a low-symmetry phase in which the polarization lies away from a highly symmetric direction typically generates phenomenal dielectric and electromechanical responses. Here, we investigate the phase transition sequence of nanowires made of KNbO(3) and BaTiO(3) perovskites, by combining X-ray diffraction, Raman spectroscopy, and first-principles-based calculations. We provide evidence of a previously unreported ferroelectric ground state of monoclinic symmetry and the tuning of the polarization's direction by varying factors inherent to the nanoscale.

Non-volatile ferroelectric control of ferromagnetism in (Ga,Mn)As.

Multiferroic structures that provide coupled ferroelectric and ferromagnetic responses are of significant interest as they may be used in novel memory devices and spintronic logic elements. One approach towards this goal is the use of composites that couple ferromagnetic and ferroelectric layers through magnetostrictive and piezoelectric strain transmitted across the interfaces. However, mechanical clamping of the films to the substrate limits their response. Structures where the magnetic response is modulated directly by the electric field of the poled ferroelectric would eliminate this constraint and provide a qualitatively higher level of integration, combining the emerging field of multiferroics with conventional semiconductor microelectronics. Here, we report the realization of such a device using (Ga,Mn)As, which is an archetypical diluted magnetic semiconductor with well-understood carrier-mediated ferromagnetism, and a polymer ferroelectric gate. Polarization reversal of the gate by a single voltage pulse results in a persistent modulation of the Curie temperature of the ferromagnetic semiconductor. The non-volatile gating of (Ga,Mn)As has been made possible by applying a low-temperature copolymer deposition technique that is distinct from pre-existing technologies for ferroelectric gates on magnetic oxides. This accomplishment opens a way to nanometre-scale modulation of magnetic semiconductor properties with rewritable ferroelectric domain patterns, operating at modest voltages and subnanosecond times.

Ferroelectricity in asymmetric metal-ferroelectric-metal heterostructures: a combined first-principles-phenomenological approach.

We present an approach to the size effect problem in ferroelectric-electrode systems which combines first-principles calculations and phenomenological theory. The parameters of the model can be extracted from calculations on ultrathin films, while experimentally verifiable predictions can be made on thick films. We illustrate the approach for the case of SrRuO3/BaTiO3/SrRuO3 heterostructures with asymmetric interfaces. This enables us to provide a quantitative description of a number of manifestations of such asymmetry in films of technologically meaningful thickness.

In-plane and out-of-plane ferroelectric instabilities in epitaxial SrTiO3 films.

The in-plane and out-of-plane ferroelectric instabilities in compressed (100)-epitaxial SrTiO3 films were examined by infrared reflection spectroscopy. The strongly stiffened in-plane soft mode frequency softened very slowly on cooling. On the other hand, the silent mode appeared at around 150 K, indicating an out-of-plane ferroelectric transition. This behavior points to a split of in-plane and out-of-plane ferroelectric instability temperatures due to the lowered symmetry of the SrTiO3 lattice caused by mechanical misfit strain. Infrared spectroscopy provides a possibility to detect such an effect in the strained epitaxial ferroelectric films.

Ionic polarizability of conductive metal oxides and critical thickness for ferroelectricity in BaTiO3.

We report a first-principles investigation of ultrathin BaTiO(3) films with SrRuO(3) electrodes. We find that the ionic relaxations in the metal-oxide electrode play a crucial role in stabilizing the ferroelectric phase. Comparison with frozen-phonon calculations shows that the degree of softness of the SrRuO(3) lattice has an essential impact on the screening of ferroelectric polarization in BaTiO(3). The critical thickness for ferroelectricity in BaTiO(3) is found to be 1.2 nm. The results of our calculations provide a possible explanation for the beneficial impact of oxide electrodes on the switching and dielectric properties of ferroelectric capacitors.

Growth of single-crystalline KNbO3 nanostructures.

This communication reports on the growth of highly uniform KNbO3 nanowires exhibiting a narrow diameter distribution around 60 nm and a length-to-width ratio up to 100. The nanowires were prepared by a hydrothermal route, which enables simple, gram-scale production. A systematic study of the synthesized nanowires in terms of the morphological and chemical characteristics was carried out by varying the temperature-pressure conditions and the composition of the starting mixture. The results indicate that highly uniform single-crystalline nanowires form within a narrow window of the ternary phase diagram of KOH-Nb2O5-H2O.

Surface-stimulated nucleation of reverse domains in ferroelectrics.

We present a model for reverse domain nucleation in ferroelectrics, which takes into account ferroelectric-electrode coupling in both homogeneous and random cases. The model provides a solution to the coercivity paradox--i.e., the large discrepancy between the observed and predicted coercive fields, common to many systems. We demonstrate the possibility of not thermally activated nucleation of reverse domains. We find that small inhomogeneities in the ferroelectric-electrode interface may lead to an exponentially wide spectrum of waiting times for switching. The model predicts that switching is facilitated near morphotropic phase boundaries in perovskite-type ferroelectrics.

Growth kinetics of one-dimensional KNbO3 nanostructures by hydrothermal processing routes.

The growth kinetics of one-dimensional single-crystalline KNbO(3) nanostructures (nanowires and nanofingers, the latter understood as defective nanowires) prepared by hydrothermal processing routes has been theoretically studied. A model taking into account the cube-based morphology of the nanostructures, their defects as the KOH proportion in the starting solution increases, and the partial depletion of species in the solution at the kink regions is proposed. Such a model allows the morphological evolution of the nanostructures to be successfully reproduced, shedding light on the origin of their highly anisotropic growth.

Soft and central mode behaviour in PbMg(1/3)Nb(2/3)O(3) relaxor ferroelectric.

The relaxor ferroelectric PbMg(1/3)Nb(2/3)O(3) (PMN) is investigated by means of dielectric and Fourier transform far infrared transmission spectroscopy in the frequency range from 10 kHz to 15 THz at temperatures between 20 and 900 K using mostly thin films on infrared transparent sapphire substrates. While the thin film relaxors display reduced dielectric permittivity at low frequencies, their high frequency lattice response is shown to be the same as for single-crystal/ceramic specimens. In contrast to the results of inelastic neutron scattering, the optic soft mode is found to be underdamped at all temperatures. On heating, the TO1 soft phonon follows the Cochran law with an extrapolated critical temperature of 670 K near to the Burns temperature. Above 450 K the soft mode frequency levels off near 50 cm(-1) and above the Burns temperature it slightly hardens. Central-mode-type dispersion assigned to the dynamics of polar nanoclusters appears below the Burns temperature at frequencies near to but below the soft mode and slows down and broadens dramatically on cooling, finally, below the freezing temperature of 200 K, giving rise to frequency independent losses from the microwave range down. A new explanation of the phonon 'waterfall' effect in inelastic neutron scattering spectra is proposed.