Observation of polar vortices in oxide superlattices.

The complex interplay of spin, charge, orbital and lattice degrees of freedom provides a plethora of exotic phases and physical phenomena. In recent years, complex spin topologies have emerged as a consequence of the electronic band structure and the interplay between spin and spin-orbit coupling in materials. Here we produce complex topologies of electrical polarization--namely, nanometre-scale vortex-antivortex (that is, clockwise-anticlockwise) arrays that are reminiscent of rotational spin topologies--by making use of the competition between charge, orbital and lattice degrees of freedom in superlattices of alternating lead titanate and strontium titanate layers. Atomic-scale mapping of the polar atomic displacements by scanning transmission electron microscopy reveals the presence of long-range ordered vortex-antivortex arrays that exhibit nearly continuous polarization rotation. Phase-field modelling confirms that the vortex array is the low-energy state for a range of superlattice periods. Within this range, the large gradient energy from the vortex structure is counterbalanced by the corresponding large reduction in overall electrostatic energy (which would otherwise arise from polar discontinuities at the lead titanate/strontium titanate interfaces) and the elastic energy associated with epitaxial constraints and domain formation. These observations have implications for the creation of new states of matter (such as dipolar skyrmions, hedgehog states) and associated phenomena in ferroic materials, such as electrically controllable chirality.

Non-Ohmic Variable-Range Hopping and Resistive Switching in SrTiO_{3} Domain Walls.

We report observation of electric field driven conductivity with negative differential conductance and resistive switching in insulating SrTiO_{3} samples over a wide range of applied voltages at low temperatures. The observed current follows I=I_{0}exp[-(E^{*}/E)^{1/2}] at large applied electric field, corresponding to variable range hopping conduction with a Coulomb gap in domain walls. Our data are sufficient to discriminate unambiguously between Shklovskii and Mott hopping via their different electric field exponent. Under some conditions space-charge-limited currents are observed, and the charge mobility limit is determined to be in the range of 17 and 210 cm^{2}/Vs.

Phonon and magnetoelastic coupling in Al0.5Ga0.5FeO3: Raman, magnetization and neutron diffraction studies.

The intriguing coupling phenomena among spin, phonon, and charge degrees of freedom in materials having magnetic, ferroelectric and/or ferroelastic order have been of research interest for the fundamental understanding and technological relevance. We report a detailed study on structure and phonons of Al0.5Ga0.5FeO3 (ALGF), a lead-free magnetoelectric material, carried out using variable temperature dependent powder neutron diffraction and Raman spectroscopy. Neutron diffraction studies suggest that Al3+ ions are distributed in one tetrahedrally (BO4) and three octahedrally (BO6) coordinated sites of the orthorhombic (Pc21n) structure and there is no structural transition in the temperature range of 7-800 K. Temperature dependent field-cooled and zero-field-cooled magnetization studies indicate ferrimagnetic ordering below 225 K (TN), and that is reflected in the low temperature powder neutron diffraction data. An antiferromagnetic type arrangement of Fe3+ ions with net magnetic moment of 0.13 µB/Fe3+ was observed from powder neutron diffraction analysis and it corroborates the findings from magnetization studies. At the magnetic transition temperature, no drastic change in lattice strain was observed, while significant changes in phonons were observed in the Raman spectra. The deviation of several mode frequencies from the standard anharmonicity model in the ferrimagnetic phase (below 240 K) is attributed to coupling effect between spin and phonon. Spin-phonon coupling effect is discernable from Raman bands located at 270, 425, 582, 695, 738, and 841 cm-1. Their coupling strengths (λ) have been estimated using our phonon spectra and magnetization results. BOn (n = 4, 6) libration (restricted rotation) mode at 270 cm-1 has the largest coupling constant (λ∼ 2.3), while the stretching vibrations located at 695 and 738 cm-1 have the lowest coupling constant (λ∼ 0.5). In addition to the libration mode, several internal stretching and bending modes of polyhedral units are strongly affected by spin ordering.

Tin titanate-the hunt for a new ferroelectric perovskite.

We review all the published literature and show that there is no experimental evidence for homogeneous tin titanate SnTiO3 in bulk or thin-film form. Instead a combination of unrelated artefacts are easily misinterpreted. The x-ray Bragg data are contaminated by double scattering from the Si substrate, giving a strong line at the 2θ angle exactly where perovskite SnTiO3 should appear. The strong dielectric divergence near 560 K is irreversible and arises from oxygen site detrapping, accompanied by Warburg/Randles interfacial anomalies. The small (4 µC cm-2) apparent ferroelectric hysteresis remains in samples shown to be pure (Sn,Ti)O2 rutile/cassiterite, in which ferroelectricity is forbidden. Only very recent work reveals real bulk SnTiO3, but it possesses an ilmenite-like structure with an elaborate array of stacking faults, not suitable for ferroelectric devices. Unpublished TEM data reveal an inhomogeneous SnO layered structured thin films, related to shell-core structures. The harsh conclusion is that there is a combination of unrelated artefacts masquerading as ferroelectricity in powders and ALD films; and only a trace of a second phase in PLD film data suggests any perovskite content at all. The fact that x-ray, dielectric, and hysteresis data all lead to the wrong conclusion is instructive and reminds us of earlier work on copper calcium titanate (a well-known boundary-layer capacitor).

Prospects and applications near ferroelectric quantum phase transitions: a key issues review.

The emergence of complex and fascinating states of quantum matter in the neighborhood of zero temperature phase transitions suggests that such quantum phenomena should be studied in a variety of settings. Advanced technologies of the future may be fabricated from materials where the cooperative behavior of charge, spin and current can be manipulated at cryogenic temperatures. The progagating lattice dynamics of displacive ferroelectrics make them appealing for the study of quantum critical phenomena that is characterized by both space- and time-dependent quantities. In this key issues article we aim to provide a self-contained overview of ferroelectrics near quantum phase transitions. Unlike most magnetic cases, the ferroelectric quantum critical point can be tuned experimentally to reside at, above or below its upper critical dimension; this feature allows for detailed interplay between experiment and theory using both scaling and self-consistent field models. Empirically the sensitivity of the ferroelectric T c's to external and to chemical pressure gives practical access to a broad range of temperature behavior over several hundreds of Kelvin. Additional degrees of freedom like charge and spin can be added and characterized systematically. Satellite memories, electrocaloric cooling and low-loss phased-array radar are among possible applications of low-temperature ferroelectrics. We end with open questions for future research that include textured polarization states and unusual forms of superconductivity that remain to be understood theoretically.

Local Electrical Imaging of Tetragonal Domains and Field-Induced Ferroelectric Twin Walls in Conducting SrTiO_{3}.

We demonstrate electrical mapping of tetragonal domains and electric field-induced twin walls in SrTiO_{3} as a function of temperature and gate bias utilizing the conducting LaAlO_{3}/SrTiO_{3} interface and low-temperature scanning electron microscopy. Conducting twin walls appear below 105 K, and new twin patterns are observed after thermal cycling through the transition or on electric field gating. The nature of the twin walls is confirmed by calculating their intersection angles for different substrate orientations. Numerous walls formed when a large side- or back-gate voltage is applied are identified as field-induced ferroelectric twin walls in the paraelectric tetragonal matrix. The walls persist after switching off the electric field and on thermal cycling below 105 K. These observations point to a new type of ferroelectric functionality in SrTiO_{3}, which could be exploited together with magnetism and superconductivity in a multifunctional context.

Correlation of dielectric, electrical and magnetic properties near the magnetic phase transition temperature of cobalt zinc ferrite.

Multiferroic composite structures, i.e., composites of magnetostrictive and piezoelectric materials, can be envisioned to achieve the goal of strong room-temperature ME coupling for real practical device applications. Magnetic materials with high magnetostriction, high Néel temperature (TN), high resistivity and large magnetization are required to observe high ME coupling in composite structures. In continuation of our investigations on suitable magnetic candidates for multiferroic composite structures, we have studied the crystal structure, dielectric, transport, and magnetic properties of Co0.65Zn0.35Fe2O4 (CZFO). Rietveld refinement of X-ray diffraction patterns confirms the phase purity with a cubic crystal structure with the (Fd3[combining macron]m) space group; however, we have found a surprisingly large magneto-dielectric anomaly at the Néel temperature, unexpected for a cubic structure. The presence of mixed valences of Fe2+/Fe3+ cations is probed by X-ray photoelectron spectroscopy (XPS), which supports the catonic ordering-mediated large dielectric response. Large dielectric permittivity dispersion with a broad anomaly is observed in the vicinity of the magnetic phase transition temperature (TN) of CZFO suggesting a strong correlation between dielectric and magnetic properties. The evidence of strong spin-polaron coupling has been established from temperature dependent dielectric, ac conductivity and magnetization studies. The ferrimagnetic-paramagnetic phase transition of CZFO has been found at ∼640 K, which is well above room temperature. CZFO exhibits low loss tangent, a high dielectric constant, large magnetization with soft magnetic behavior and magnetodielectric coupling above room temperature, elucidating the possible potential candidates for multiferroic composite structures as well as for multifunctional and spintronics device applications.

High-symmetry polarization domains in low-symmetry ferroelectrics.

We present experimental evidence for polygonal domain faceting in the ferroelectric polymer poly(vinylidene fluoride-trifluoroethylene) (PVDF-TrFE) films with the lower orthorhombic crystallographic symmetry. It is proposed that this effect can arise from purely electrostatic depolarizing forces. We show that, in contrast to magnetic bubble shape domains, where such type of deformation instability has a predominantly elliptical character, the emergence of more symmetrical circular harmonics is favored in ferroelectrics with high dielectric constants.

Studies of the Room-Temperature Multiferroic Pb(Fe0.5Ta0.5)0.4(Zr0.53Ti0.47)0.6O3: Resonant Ultrasound Spectroscopy, Dielectric, and Magnetic Phenomena.

Recently, lead iron tantalate/lead zirconium titanate (PZTFT) was demonstrated to possess large, but unreliable, magnetoelectric coupling at room temperature. Such large coupling would be desirable for device applications but reproducibility would also be critical. To better understand the coupling, the properties of all 3 ferroic order parameters, elastic, electric, and magnetic, believed to be present in the material across a range of temperatures, are investigated. In high temperature elastic data, an anomaly is observed at the orthorhombic mm2 to tetragonal 4mm transition, Tot = 475 K, and a softening trend is observed as the temperature is increased toward 1300 K, where the material is known to become cubic. Thermal degradation makes it impossible to measure elastic behavior up to this temperature, however. In the low temperature region, there are elastic anomalies near ≈40 K and in the range 160-245 K. The former is interpreted as being due to a magnetic ordering transition and the latter is interpreted as a hysteretic regime of mixed rhombohedral and orthorhombic structures. Electrical and magnetic data collected below room temperature show anomalies at remarkably similar temperature ranges to the elastic data. These observations are used to suggest that the three order parameters in PZTFT are strongly coupled.

Tunneling electroresistance in multiferroic heterostructures.

We demonstrate the room temperature polar switching and tunneling in PbZr0.52Ti0.48O3 (PZT) ultra-thin films of thickness 3-7 nm, sandwiched between platinum metal and ferromagnetic La0.67Sr0.33MnO3 (LSMO) layers, which also shows magnetic field dependent tunnel current switching in Pt/PbZr0.52Ti0.48O3/La0.67Sr0.33MnO3 heterostructures. The epitaxial nature, surface quality and ferroelectric switching of heterostructured films were examined with the help of x-ray diffraction patterns, atomic force microscopy, and piezo force microscopy, respectively. The capacitance versus voltage graphs show butterfly loops above the coercive field (> ±3 V) of PZT for small probe area (∼16 µm(2)). The effect of ferroelectric switching was observed in current density versus voltage curves with a large variation in high-resistance/low-resistance (HRS/LRS) ratio (2:1 to 100:1), however, these effects were more prominent in the presence of in-plane external magnetic field. The conductance is fitted with Brinkman's model, and the parabolic conductance upon bias voltage implies electron tunneling governs the transport.

Self-similar nested flux closure structures in a tetragonal ferroelectric.

In specific solid-state materials, under the right conditions, collections of magnetic dipoles are known to spontaneously form into a variety of rather complex geometrical patterns, exemplified by vortex and skyrmion structures. While theoretically, similar patterns should be expected to form from electrical dipoles, they have not been clearly observed to date: the need for continued experimental exploration is therefore clear. In this Letter we report the discovery of a rather complex domain arrangement that has spontaneously formed along the edges of a thin single crystal ferroelectric sheet, due to surface-related depolarizing fields. Polarization patterns are such that nanoscale "flux-closure" loops are nested within a larger mesoscale flux closure object. Despite the orders of magnitude differences in size, the geometric forms of the dual-scale flux closure entities are rather similar.

Domains within domains and walls within walls: evidence for polar domains in cryogenic SrTiO3.

Resonant piezoelectric spectroscopy shows polar resonances in paraelectric SrTiO3 at temperatures below 80 K. These resonances become strong at T<40 K. The resonances are induced by weak electric fields and lead to standing mechanical waves in the sample. This piezoelectric response does not exist in paraelastic SrTiO3 nor at temperatures just below the ferroelastic phase transition. The interpretation of the resonances is related to ferroelastic twin walls which become polar at low temperatures in close analogy with the known behavior of CaTiO3. SrTiO3 is different from CaTiO3, however, because the wall polarity is thermally induced; i.e., there exists a small temperature range well below the ferroelastic transition point at 105 K where polarity appears on cooling. As the walls are atomistically thin, this transition has the hallmarks of a two-dimensional phase transition restrained to the twin boundaries rather than a classic bulk phase transition.

Manipulating ferroelectric domains in nanostructures under electron beams.

Freestanding BaTiO3 nanodots exhibit domain structures characterized by distinct quadrants of ferroelastic 90° domains in transmission electron microscopy (TEM) observations. These differ significantly from flux-closure domain patterns in the same systems imaged by piezoresponse force microscopy. Based upon a series of phase field simulations of BaTiO3 nanodots, we suggest that the TEM patterns result from a radial electric field arising from electron beam charging of the nanodot. For sufficiently large charging, this converts flux-closure domain patterns to quadrant patterns with radial net polarizations. Not only does this explain the puzzling patterns that have been observed in TEM studies of ferroelectric nanodots, but also suggests how to manipulate ferroelectric domain patterns via electron beams.

Emerging memories: resistive switching mechanisms and current status.

The resistance switching behaviour of several materials has recently attracted considerable attention for its application in non-volatile memory (NVM) devices, popularly described as resistive random access memories (RRAMs). RRAM is a type of NVM that uses a material(s) that changes the resistance when a voltage is applied. Resistive switching phenomena have been observed in many oxides: (i) binary transition metal oxides (TMOs), e.g. TiO(2), Cr(2)O(3), FeO(x) and NiO; (ii) perovskite-type complex TMOs that are variously functional, paraelectric, ferroelectric, multiferroic and magnetic, e.g. (Ba,Sr)TiO(3), Pb(Zr(x) Ti(1-x))O(3), BiFeO(3) and Pr(x)Ca(1-x)MnO(3); (iii) large band gap high-k dielectrics, e.g. Al(2)O(3) and Gd(2)O(3); (iv) graphene oxides. In the non-oxide category, higher chalcogenides are front runners, e.g. In(2)Se(3) and In(2)Te(3). Hence, the number of materials showing this technologically interesting behaviour for information storage is enormous. Resistive switching in these materials can form the basis for the next generation of NVM, i.e. RRAM, when current semiconductor memory technology reaches its limit in terms of density. RRAMs may be the high-density and low-cost NVMs of the future. A review on this topic is of importance to focus concentration on the most promising materials to accelerate application into the semiconductor industry. This review is a small effort to realize the ambitious goal of RRAMs. Its basic focus is on resistive switching in various materials with particular emphasis on binary TMOs. It also addresses the current understanding of resistive switching behaviour. Moreover, a brief comparison between RRAMs and memristors is included. The review ends with the current status of RRAMs in terms of stability, scalability and switching speed, which are three important aspects of integration onto semiconductors.

Domain wall damping and elastic softening in SrTiO3: evidence for polar twin walls.

A marked change in anelastic properties, namely, elastic softening accompanied by increased damping, has been observed in a single crystal of SrTiO(3) below ~50 K by resonant ultrasound spectroscopy. This correlates with other subtle changes in structure and properties which have been explained in the past in terms of a novel quantum state and the formation of polar clusters in an incipient ferroelectric structure. Comparison of the new data, obtained at frequencies near 1 MHz, with mechanical spectroscopy data collected at a few Hz or a few kHz, reveals a distinct dispersion with frequency and is interpreted in terms of an acoustic loss mechanism which depends primarily on the mobility under stress of ferroelastic twin walls. In most ferroelastic materials, it is found that the twin walls become immobile below some low-temperature interval due to the pinning effects of defects. It is proposed instead for SrTiO(3) that associated with the local atomic displacements within the incipient ferroelectric clusters is a change in structure of the twin walls such that their mobility becomes enhanced. We propose that the structural change is not correlated with structural changes of the bulk material but relates to increasing polarity of the walls. This interpretation implies that ferroelastic domain walls in SrTiO(3) become ferroelectric at low temperatures.