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Jim Scott was a larger-than-life figure who performed pioneering academic and commercial research, mainly on Raman spectroscopy, ferroelectrics, and multiferroics. His career developed at the same time as methodological advances were being made in thin-film deposition and in growth and patterning of complex nanoscale materials. Such advances gave him the opportunity to lead the charge in the integration of ferroelectric oxide films with semiconductors for microwave antennae (predominantly for mobile phones), and in the creation and integration of thin-film capacitor structures for ferroelectric random access memory (FeRAM) chips. He made particularly noteworthy contributions in overcoming the fatigue problem, critical to FeRAM technology. He also played a central role in pushing nanoscale ferroelectrics beyond thin films and into three-dimensional geometries and was an important figure in the birth, and in the renaissance, of magnetoelectric multiferroics. Like many great scientists, Jim was adept at spotting connections between seemingly unconnected topics, establishing new conceptual frameworks and discovering new phenomena that were often received sceptically at first and then embraced by the community.

Simultaneous manipulation of multiple boundary conditions in nanoscale heterostructures offers a versatile route to stabilizing unusual structures and emergent phases. Here, we show that a stable supercrystal phase comprising a three-dimensional ordering of nanoscale domains with tailored periodicities can be engineered in PbTiO3–SrRuO3 ferroelectric–metal superlattices. A combination of laboratory and synchrotron X-ray diffraction, piezoresponse force microscopy, scanning transmission electron microscopy and phase-field simulations reveals a complex hierarchical domain structure that forms to minimize the elastic and electrostatic energy. Large local deformations of the ferroelectric lattice are accommodated by periodic lattice modulations of the metallic SrRuO3 layers with curvatures up to 107 m−1. Our results show that multidomain ferroelectric systems can be exploited as versatile templates to induce large curvatures in correlated materials, and present a route for engineering correlated materials with modulated structural and electronic properties that can be controlled using electric fields. Ferroelectric superlattices can present a rich variety of phenomena. Here, in PbTiO3/SrRuO3 superlattices, it is shown that a complex and stable hierarchical supercrystal can form, with the correlated metal of the SrRuO3 layers showing large curvatures.

Ferroelectrics subject to suitable electric boundary conditions present a steady negative capacitance response1,2. When the ferroelectric is in a heterostructure, this behaviour yields a voltage amplification in the other elements, which experience a potential difference larger than the one applied, holding promise for low-power electronics3. So far research has focused on verifying this effect and little is known about how to optimize it. Here, we describe an electrostatic theory of ferroelectric/dielectric superlattices, convenient model systems4,5, and show the relationship between the negative permittivity of the ferroelectric layers and the voltage amplification in the dielectric ones. Then, we run simulations of PbTiO3/SrTiO3 superlattices to reveal the factors most strongly affecting the amplification. In particular, we find that giant effects (up to tenfold increases) can be obtained when PbTiO3 is brought close to the so-called ‘incipient ferroelectric’ state.

The capacitor is a key element of electronic devices and is characterized by positive capacitance. However, a negative capacitance (NC) behaviour may occur in certain cases and implies a local voltage drop opposed to the overall applied bias. Therefore, a local NC response results in voltage enhancement across the rest of the circuit. Within a suitably designed heterostructure, ferroelectrics display such an NC effect, and various ferroelectric-based microelectronic and nanoelectronic devices have been developed, showing improved performance attributed to NC. However, the exact physical nature of the NC response and direct experimental evidence remain elusive or controversial thus far. In this Review, we discuss the physical mechanisms responsible for ferroelectric NC, tackling static and transient NC responses. We examine ferroelectric responses to voltage and charge, as well as ferroelectric switching, and discuss proof-of-concept experiments and possibilities for device implementation. Finally, we highlight different approaches for the optimization of the intrinsic NC response to maximize voltage amplification. Ferroelectrics-based materials can display a negative capacitance (NC) effect, providing an opportunity to implement NC in electronic circuits to improve their performance. In this Review, the authors discuss static and transient NC responses in ferroelectrics and highlight proof-of-concept experiments and possibilities for device implementation.

$\mathrm{Pb}\mathrm{Ti}{\mathrm{O}}_{3}/\mathrm{Sr}\mathrm{Ru}{\mathrm{O}}_{3}$ superlattices deposited on $\mathrm{Sr}\mathrm{Ti}{\mathrm{O}}_{3}$ substrates are studied using a combination of x-ray diffraction, piezoresponse force microscopy, scanning transmission electron microscopy, transport measurements, and impedance spectroscopy. The superlattices are found to have two inequivalent interfaces resulting from differences in the growth modes for $\mathrm{Pb}\mathrm{Ti}{\mathrm{O}}_{3}$ and $\mathrm{Sr}\mathrm{Ru}{\mathrm{O}}_{3}$. X-ray diffraction measurements show that, despite being sandwiched between metallic $\mathrm{Sr}\mathrm{Ru}{\mathrm{O}}_{3}$ layers, the ferroelectric layers possess dense nanoscale domains. The observed domain sizes are comparable to those found in ferroelectric-dielectric systems, and they are attributed to the depolarizing field caused by the finite screening length of the $\mathrm{Sr}\mathrm{Ru}{\mathrm{O}}_{3}\ensuremath{-}\mathrm{Pb}\mathrm{Ti}{\mathrm{O}}_{3}$ interface. The macroscopic capacitance of the ultrathin $\mathrm{Pb}\mathrm{Ti}{\mathrm{O}}_{3}$ layers was measured, and its temperature dependence was found to be consistent with permittivity enhancement due to domain wall motion.

The combination of strain and electrostatic engineering in epitaxial heterostructures of ferroelectric oxides offers many possibilities for inducing new phases, complex polar topologies, and enhanced electrical properties. However, the dominant effect of substrate clamping can also limit the electromechanical response and often leaves electrostatics to play a secondary role. Releasing the mechanical constraint imposed by the substrate can not only dramatically alter the balance between elastic and electrostatic forces, enabling them to compete on par with each other, but also activate new mechanical degrees of freedom, such as the macroscopic curvature of the heterostructure. In this work, an electrostatically driven transition from a predominantly out-of-plane polarized to an in-plane polarized state is observed when a PbTiO3 /SrTiO3 superlattice with a SrRuO3 bottom electrode is released from its substrate. In turn, this polarization rotation modifies the lattice parameter mismatch between the superlattice and the thin SrRuO3 layer, causing the heterostructure to curl up into microtubes. Through a combination of synchrotron-based scanning X-ray diffraction imaging, Raman scattering, piezoresponse force microscopy and scanning transmission electron microscopy, the crystalline structure and domain patterns of the curved superlattices are investigated, revealing a strong anisotropy in the domain structure and a complex mechanism for strain accommodation. This article is protected by copyright. All rights reserved.

Obituario.

Simultaneous manipulation of multiple boundary conditions in nanoscale heterostructures offers a versatile route to stabilizing unusual structures and emergent phases. Here, we show that a stable supercrystal phase comprising a three-dimensional ordering of nanoscale domains with tailored periodicities can be engineered in PbTiO

Strongly correlated materials show unique solid-state phase transitions with rich nanoscale phenomenology that can be controlled by external stimuli. Particularly interesting is the case of light–matter interaction in the proximity of the metal–insulator transition of heteroepitaxial nickelates. In this work, we use near-infrared laser light in the high-intensity excitation regime to manipulate the nanoscale phase separation in NdNiO3. By tuning the laser intensity, we can reproducibly set the coverage of insulating nanodomains, which we image by photoemission electron microscopy, thus semipermanently configuring the material state. With the aid of transport measurements and finite element simulations, we identify two different timescales of thermal dynamics in the light–matter interaction: a steady-state and a fast transient local heating. These results open interesting perspectives for locally manipulating and reconfiguring electronic order at the nanoscale by optical means.

Tungsten trioxide $({\mathrm{WO}}_{3})$ is a versatile material with widespread applications ranging from electrochromics and optoelectronics to water splitting and catalysis of chemical reactions. For technological applications, thin films of ${\mathrm{WO}}_{3}$ are particularly appealing, taking advantage from a high surface-to-volume ratio and tunable physical properties. However, the growth of stoichiometric crystalline thin films is challenging because the deposition conditions are very sensitive to the formation of oxygen vacancies. In this paper, we show how background oxygen pressure during pulsed laser deposition can be used to tune the structural and electronic properties of ${\mathrm{WO}}_{3}$ thin films. By performing x-ray diffraction and low-temperature electrical transport measurements, we find changes in the ${\mathrm{WO}}_{3}$ lattice volume of up to 10% concomitantly with a resistivity drop of more than five orders of magnitude at room temperature as a function of increased oxygen deficiency. We use advanced ab initio calculations to describe in detail the properties of the oxygen vacancy defect states and their evolution in terms of excess charge concentration. Our results depict an intriguing scenario where structural, electronic, optical, and transport properties of ${\mathrm{WO}}_{3}$ single-crystal thin films can all be purposely tuned by controlling the oxygen vacancy formation during growth.

Ferroelectric domains in PbTiO_{3}/SrTiO_{3} superlattices are studied using synchrotron x-ray diffraction. Macroscopic measurements reveal a change in the preferential domain wall orientation from {100} to {110} crystallographic planes with increasing temperature. The temperature range of this reorientation depends on the ferroelectric layer thickness and domain period. Using a nanofocused beam, local changes in the domain wall orientation within the buried ferroelectric layers are imaged, both in structurally uniform regions of the sample and near defect sites and argon ion-etched patterns. Domain walls are found to exhibit a preferential alignment with the straight edges of the etched patterns as well as with structural features associated with defect sites. The distribution of out-of-plane lattice parameters is mapped around one such feature, showing that it is accompanied by inhomogeneous strain and large strain gradients.

The instability of ferroelectric ordering in ultra-thin films is one of the most important fundamental issues pertaining realization of a number of electronic devices with enhanced functionality, such as ferroelectric and multiferroic tunnel junctions or ferroelectric field effect transistors. In this paper, we investigate the polarization state of archetypal ultrathin (several nanometres) ferroelectric heterostructures: epitaxial single-crystalline BaTiO

Polydomain superlattices composed of ferroelectric PbTiO3 and paraelectric SrTiO3 were investigated by means of temperature-dependent X-ray diffraction and electrical measurements. The ferroelectric nanodomains were found to have an almost isotropic distribution of domain wall alignments and to be highly responsive to applied electric fields, giving rise to large enhancements in the overall dielectric response of the structure. Electrical measurements revealed a dramatic dependence of the dielectric permittivity, tunability, and polarization-voltage characteristics on the superlattice period. For short-period superlattices, double hysteresis loops were observed.

Complex transition metal oxides span a wide range of crystalline structures and play host to an incredible variety of physical phenomena. High dielectric permittivities, piezo-, pyro-, and ferroelectricity are just a few of the functionalities offered by this class of materials, while the potential for applications of the more exotic properties like high temperature superconductivity and colossal magnetoresistance is still waiting to be fully exploited. With recent advances in deposition techniques, the structural quality of oxide heterostructures now rivals that of the best conventional semiconductors, taking oxide electronics to a new level. Such heterostructures have enabled the fabrication of artificial multifunctional materials. At the same time they have exposed a wealth of phenomena at the boundaries where compounds with different structural instabilities and electronic properties meet, giving unprecedented access to new physics emerging at oxide interfaces. Here we highlight some of these exciting new interface phenomena.

The metal-insulator transitions and the intriguing physical properties of rare-earth perovskite nickelates have attracted considerable attention in recent years. Nonetheless, a complete understanding of these materials remains elusive. Here, taking a NdNiO3 thin film as a representative example, we utilize a combination of x-ray absorption and resonant inelastic x-ray scattering (RIXS) spectroscopies to resolve important aspects of the complex electronic structure of the rare-earth nickelates. The unusual coexistence of bound and continuum excitations observed in the RIXS spectra provides strong evidence for the abundance of oxygen 2p holes in the ground state of these materials. Using cluster calculations and Anderson impurity model interpretation, we show that these distinct spectral signatures arise from a Ni 3d8 configuration along with holes in the oxygen 2p valence band, confirming suggestions that these materials do not obey a conventional positive charge-transfer picture, but instead exhibit a negative charge-transfer energy, in line with recent models interpreting the metal to insulator transition in terms of bond disproportionation., 27 pages, 6 figures

Nucleation processes of mixed-phase states are an intrinsic characteristic of first-order phase transitions, typically related to local symmetry breaking. Direct observation of emerging mixed-phase regions in materials showing a first-order metal–insulator transition (MIT) offers unique opportunities to uncover their driving mechanism. Using photoemission electron microscopy, we image the nanoscale formation and growth of insulating domains across the temperature-driven MIT in NdNiO3 epitaxial thin films. Heteroepitaxy is found to strongly determine the nanoscale nature of the phase transition, inducing preferential formation of striped domains along the terraces of atomically flat stepped surfaces. We show that the distribution of transition temperatures is a local property, set by surface morphology and stable across multiple temperature cycles. Our data provide new insights into the MIT of heteroepitaxial nickelates and point to a rich, nanoscale phenomenology in this strongly correlated material., Probing the evolution of mixed-phase states in materials offers unique insights into the microscopic mechanism of phase transitions. Here, Mattoni et al. report imaging of nanoscale formation and growth of insulating domains across the metal-insulator transition in NdNiO3 thin films, uncovering a rich interplay between structural and electronic degrees of freedom.

The stability of spontaneous electrical polarization in ferroelectrics is fundamental to many of their current applications, which range from the simple electric cigarette lighter to non-volatile random access memories1. Research on nanoscale ferroelectrics reveals that their behaviour is profoundly different from that in bulk ferroelectrics, which could lead to new phenomena with potential for future devices2, 3, 4. As ferroelectrics become thinner, maintaining a stable polarization becomes increasingly challenging. On the other hand, intentionally destabilizing this polarization can cause the effective electric permittivity of a ferroelectric to become negative5, enabling it to behave as a negative capacitance when integrated in a heterostructure. Negative capacitance has been proposed as a way of overcoming fundamental limitations on the power consumption of field-effect transistors6. However, experimental demonstrations of this phenomenon remain contentious7. The prevalent interpretations based on homogeneous polarization models are difficult to reconcile with the expected strong tendency for domain formation8, 9, but the effect of domains on negative capacitance has received little attention5, 10, 11, 12. Here we report negative capacitance in a model system of multidomain ferroelectric–dielectric superlattices across a wide range of temperatures, in both the ferroelectric and paraelectric phases. Using a phenomenological model, we show that domain-wall motion not only gives rise to negative permittivity, but can also enhance, rather than limit, its temperature range. Our first-principles-based atomistic simulations provide detailed microscopic insight into the origin of this phenomenon, identifying the dominant contribution of near-interface layers and paving the way for its future exploitation.

A summary is presented of recent developments in ferroelectric nanotubes, nanowires and nanodots, their electrical characterization and related theories of their structures, including the possibility of toroidal ordering. Also summarized is recent work on ultra-thin single crystals and a status report on thin films, particularly in [3D] configurations for DRAM or FRAM trenched capacitors.

The focused ion beam microscope has been used to make thin lamellae and nanoscale washers from single crystals of BaTiO3. The thin lamellae were used as the dielectric layers in ‘thin film’ capacitor heterostructures, and investigated for their functional behaviour. This gave insight into the dielectric properties of thin film ferroelectrics without the usual influences of substrate clamping, grain boundaries, through film microstructural and defect chemistry variation, and inherent asymmetry associated with the electrode-dielectric boundary conditions. In essence the investigation allowed the inherent dielectric response of thin film ferroelectrics to be examined. It was found that, unlike any conventionally grown thin film capacitor heterostructures made to date, the single crystal lamellae demonstrated bulk-like functional behaviour down to a thickness of∼75nm. The fabrication of nanoscalewashers, or doughnuts, has allowed an investigation into the kinds of domain configurations that occur in highly constrained and surface-dominated 3 Dimensional architectures using Scanning Transmission Electron Microscopy. Initial work shows the existence of ‘herringbone’ domain structures which look to be shape or field compensating.

A review is given of ceramic and single-crystal thin film ferroelectric oxides, emphasizing perovskite phases, together with some new developments on hafnia films. It is shown that single-crystal barium titanate films behave as bulk down to at least 77 nm, with no finite size effects, no phase transition temperature shifts, and no dielectric peak broadening or change from first- to second-order transitions, suggesting that the gradient defect model of Bratkovsky and Levanyuk correctly describes such effects as extrinsic in experimental studies of equally thin ceramic thin films. In ceramic barium–strontium titanate (BST) thin films, it is shown that there is also no intrinsic broadening or shifts in phase transitions, with sharp, unshifted, bulk-like transitions observed only as re-entrant upon warming from cryogenic temperatures; this shows that phase transitions in ceramic thin films are dominated by kinetics and not thermodynamics and are definitely not equilibrium measurements. At high fields (>1 GV/m), the films exhibit space charge-limited conduction; no variable-range hopping is observed, contrary to recent studies on SrTiO3. Some novel, unconventional switching processes are discussed, comparing the “perimeter effect” (non-equilibrium, ballistic) with Molotskii's equilibrium model. Theory and experiment are described for [3D] nanotubes, nanorods, and nano-ribbons (or micro-ribbons). The layered-structure-perovskite–pyrochlore conversion in bismuth titanate is described together with the PbO+TiO2 phase separation in lead zirconate titanate during electrical breakdown, as are novel HfO2 precursors that demonstrate enhanced temperature crystallization from the amorphous state and hence commercial advantages for front-end processing.

Static strain in complex oxide heterostructures has been extensively used to engineer electronic and magnetic properties at equilibrium. In the same spirit, deformations of the crystal lattice with light may be used to achieve functional control across hetero-interfaces dynamically. Here, by exciting large amplitude infrared-active vibrations in a LaAlO3 substrate we induce magnetic order melting in a NdNiO3 film across a hetero-interface. Femtosecond Resonant Soft X-ray Diffraction is used to determine the spatial and temporal evolution of the magnetic disordering. We observe a magnetic melt front that grows from the substrate interface into the film, at a speed that suggests electronically driven propagation. Light control and ultrafast phase front propagation at hetero-interfaces may lead to new opportunities in optomagnetism, for example by driving domain wall motion to transport information across suitably designed devices., Comment: 35 pages, 8 Figures (both incl. Supplement)

International audience; The functional properties of oxide heterostructures ultimately rely on how the electronic and structural mismatches occurring at interfaces are accommodated by the chosen materials combination. We discuss here LaMnO$_3$/LaNiO$_3$ heterostructures, which display an intrinsic interface structural asymmetry depending on the growth sequence. Using a variety of synchrotron-based techniques, we show that the degree of intermixing at the monolayer scale allows interface-driven properties such as charge transfer and the induced magnetic moment in the nickelate layer to be controlled. Further, our results demonstrate that the magnetic state of strained LaMnO$_3$ thin films dramatically depends on interface reconstructions.

The screening efficiency of a metal-ferroelectric interface plays a critical role in determining the polarization stability and hence the functional properties of ferroelectric thin films. Imperfect screening leads to strong depolarization fields that reduce the spontaneous polarization or drive the formation of ferroelectric domains. We demonstrate that by modifying the screening at the metal-ferroelectric interface through insertion of ultrathin dielectric spacers, the strength of the depolarization field can be tuned and thus used to control the formation of nanoscale domains. Using piezoresponse force microscopy, we follow the evolution of the domain configurations as well as polarization stability as a function of depolarization field strength., Comment: 19 pages, 7 figures

We use femtosecond Resonant Soft X-ray Diffraction to observe heterogeneous melting of antiferromagnetic order in an epitaxially grown NdNiO3 film. Cross-interface coupling launches a propagating phase front following direct lattice excitation of the LaAlO3 substrate.

Using ultrafast resonant soft x ray diffraction we demonstrate photoinduced melting of antiferromagnetic order in the correlated electron insulator NdNiO3. Time dependent analysis of the resonant diffraction spectra allows us to follow the temporal evolution of the charge imbalance between adjacent Ni sites. A direct correlation between the melting of magnetic order and charge rebalancing is found. Furthermore we demonstrate that the magnetic ordering on the Ni and Nd sites which are locked together in equilibrium become decoupled during this nonthermal process. © 2013 American Physical Society.

Flexoelectricity-the coupling between polarization and strain gradients-is a universal effect allowed by symmetry in all materials. Following its discovery several decades ago, studies of flexoelectricity in solids have been scarce due to the seemingly small magnitude of this effect in bulk samples. The development of nanoscale technologies, however, has renewed the interest in flexoelectricity, as the large strain gradients often present at the nanoscale can lead to strong flexoelectric effects. Here we review the fundamentals of the flexoelectric effect in solids, discuss its presence in many nanoscale systems, and look at potential applications of this electromechanical phenomenon. The review also emphasizes the many open questions and unresolved issues in this developing field. © Copyright © 2013 by Annual Reviews. All rights reserved., The authors gratefully acknowledge funding from the Swiss National Science Foundation (A.K.T. and P.Z.), from MaNEP (P.Z.), from a European Research Council Starting Grant (G.C.), and from the Leverhulme Trust (G.C. and P.Z.).

We present a detailed study of compressively strained PbxSr1−xTiO3 thin films grown by off-axis radio frequency magnetron sputtering on (001)-oriented Nb-doped SrTiO3 substrates. Film tetragonality and the ferroelectric critical temperatures are measured for samples of different composition and thickness and compared with a phenomenological Landau-Devonshire model. 180∘ ferroelectric domains are observed using both X-ray diffraction and piezoresponse force microscopy and domain sizes obtained by the two techniques are compared and discussed.

The performance of ferroelectric devices is intimately entwined with the structure and dynamics of ferroelectric domains. In ultrathin ferroelectrics, ordered nanodomains arise naturally in response to the presence of a depolarizing field and give rise to highly inhomogeneous polarization and structural profiles. Ferroelectric superlattices offer a unique way of engineering the desired nanodomain structure by modifying the strength of the electrostatic interactions between different ferroelectric layers. Through a combination of X-ray diffraction, transmission electron microscopy, and first-principles calculations, the electrostatic coupling between ferroelectric layers is studied, revealing the existence of interfacial layers of reduced tetragonality attributed to inhomogeneous strain and polarization profiles associated with the domain structure.

The wide spectrum of exotic properties exhibited by transition-metal oxides stems from the complex competition between several quantum interactions. The capacity to select the emergence of specific phases at will is nowadays extensively recognized as key for the design of diverse new devices with tailored functionalities. In this context, interface engineering in complex oxide heterostructures has developed into a flourishing field, enabling not only further tuning of the exceptional properties of these materials, but also giving access to hidden phases and emergent physical phenomena. Here we demonstrate how interfacial interactions can induce a complex magnetic structure in a non-magnetic material. We specifically show that exchange bias can unexpectedly emerge in heterostructures consisting of paramagnetic LaNiO3 (LNO) and ferromagnetic LaMnO3 (LMO). The observation of exchange bias in (111)-oriented LNO-LMO superlattices, manifested as a shift of the magnetization-field loop, not only implies the development of interface-induced magnetism in the paramagnetic LNO layers, but also provides us with a very subtle tool for probing the interfacial coupling between the LNO and LMO layers. First-principles calculations indicate that this interfacial interaction may give rise to an unusual spin order, resembling a spin-density wave, within the LNO layers.

We report on ultrafast optical experiments in which femtosecond midinfrared radiation is used to excite the lattice of complex oxide heterostructures. By tuning the excitation energy to a vibrational mode of the substrate, a long-lived five-order-of-magnitude increase of the electrical conductivity of NdNiO3 epitaxial thin films is observed as a structural distortion propagates across the interface. Vibrational excitation, extended here to a wide class of heterostructures and interfaces, may be conducive to new strategies for electronic phase control at THz repetition rates.

The local structural distortions in polydomain ferroelectric PbTiO${}_{3}$/SrTiO${}_{3}$ superlattices are investigated by means of high spatial and energy resolution electron-energy-loss spectroscopy combined with high-angle annular dark field imaging. Local structural variations across the interfaces have been identified with unit-cell resolution through the analysis of the energy-loss near-edge structure of the Ti ${L}_{2,3}$ and O $K$ edges. Ab initio and multiplet calculations of the Ti ${L}_{2,3}$ edges provide unambiguous evidence for an inhomogeneous polarization profile associated with the observed structural distortions across the superlattice.

Transport in ultrathin films of LaNiO3 evolves from a metallic to a strongly localized character as the film's thickness is reduced and the sheet resistance reaches a value close to h/e2, the quantum of resistance in two dimensions. In the intermediate regime, quantum corrections to the Drude low- temperature conductivity are observed; they are accurately described by weak localization theory. Remarkably, the negative magnetoresistance in this regime is isotropic, which points to magnetic scattering associated with the proximity of the system to either a spin glass state or the charge ordered antiferromagnetic state observed in other rare earth nickelates., 4 pages, 4 figures, accepted for publication in PRL

4 páginas, 3 figuras.-- et al., Reversible electric-field control of the metal-insulator transition in the rare earth nickelate compound NdNiO3 is demonstrated. Using the electric double layer technique, giant modulations in the conductance as well as large shifts in the transition temperature are obtained., This work was supported by the Swiss National Science Foundation through the National Center of Competence in Research, Materials with Novel Electronic Properties, ‘MaNEP’, division II, Oxides and partly by NEDO and by Grant-in-Aid for Scientifi c Research (Grant No. 20740213) from MEXT.

The dielectric response of ${\mathrm{PbTiO}}_{3}/{\mathrm{SrTiO}}_{3}$ superlattices is studied using electrical and structural measurements. While the dielectric response of paraelectric superlattices is well accounted for by the lattice contribution, superlattices with ferroelectric compositions exhibit an enhanced permittivity. X-ray diffraction allowed the presence of ordered nanodomains in ferroelectric superlattices to be established and their displacement under an applied bias to be directly probed, demonstrating that the enhanced permittivity in these artificial materials is due to domain wall motion.

Piezoelectricity is inherent only in noncentrosymmetric materials, but a piezoelectric response can also be obtained in centrosymmetric crystals if subjected to inhomogeneous deformation. This phenomenon, known as flexoelectricity, affects the functional properties of insulators, particularly thin films of high permittivity materials. We have measured strain-gradient-induced polarization in single crystals of paraelectric SrTiO$_3$ as a function of temperature and orientation down to and below the 105 K phase transition. Estimates were obtained for all the components of the flexoelectric tensor, and calculations based on these indicate that local polarization around defects in SrTiO$_3$ may exceed the largest ferroelectric polarizations. A sign reversal of the flexoelectric response detected below the phase transition suggests that the ferroelastic domain walls of SrTiO$_3$ may be polar., 4 pages, 3 figures, 1 table

International audience; Bulk NdNiO$_3$ and thin films grown along the pseudocubic (001)$_{pc}$ axis display a 1st order metal to insulator transition (MIT) together with a Néel transition at T = 200 K. Here, we show that for NdNiO$_3$ films deposited on (111)$_{pc}$ NdGaO$_3$, the MIT occurs at T = 335 K and the Néel transition at T = 230 K. By comparing transport and magnetic properties of layers grown on substrates with different symmetries and lattice parameters, we demonstrate a particularly large tuning when the epitaxy is realized on (111)$_{pc}$ surfaces. We attribute this effect to the specific lattice matching conditions imposed along this direction when using orthorhombic substrates.

Current transients J(E,t,T) at high fields (E > 1 MV/cm) have been measured in SrTiO/sub 3/ crystals. The results are complex, with more than one transient peak time t/sub p/. t/sub p/ varies from ca. 100 ms to 100 s as a function of temperature T and voltage V. One peak displays the dependence t/sub p/=const. x (1/V) expected for the Many-Mark-Helfish cusp and may be due to space-charge-limited ionic conduction. The second peak is nearly voltage-independent and may arise from the Cox-Tredgold mechanism in which irreversible electrolytic reactions occur at the anode that facilitate hole injection. Both processes depend strongly upon the sample history.

A summary is given of probable electret effects in lead zirconate titanate (PZT), strontium titanate, polyvinylidene fluoride (PVDF), and ZnO:Li. Effects in capacitors in thin-film ferroelectric random access memories (FRAMs) such as imprint, retention, and fatigue can involve electret mechanisms and are exacerbated with radiation damage.

We present current-voltage studies of very thin (ca. 77 nm) barium titanate single crystals up to 1.3 GV/m applied field. These show that the mechanism of leakage current at high fields is that of space charge limited conduction (SCLC) in a regime with a continuous distribution of traps, according to the original model of Rose [Phys. Rev. 97, 1537 (1955)]. This study represents a factor of x5 in field compared with the early studies of BaTiO3 conduction [A. Branwood et al., Proc. Phys. Soc. London 79, 1161 (1962)]. Comparison is also given with ceramic multilayer barium titanate capacitors, which show similar SCLC behaviour. The data are shown to be completely incompatible with variable range hopping [B. I. Shklovskii, Sov. Phys. Semicond. 6, 1964 (1973)], despite the recent report of such mechanism in SrTiO3 films [D. Fuchs, M. Adam, and R. Schneider, J. Phys. IV France 11, 71 (2001)].

International audience; Nickelates are known for their metal to insulator transition (MIT) and an unusual magnetic ordering, occurring at T=T Néel. Here, we investigate thin films of SmNiO 3 subjected to different levels of epitaxial strain. We find that the original bulk behavior (T Néel

Going down to the limit of ultrathin films holds promise for a new generation of devices such as ferroelectric tunnel junctions or resistive memories. However, these length scales also make the devices sensitive to parasitic effects related to miniaturization, and a better understanding of what happens as size is reduced is of practical importance for the future development of these devices. As the experimental advances in materials preparation and characterization have come together with great progress in theoretical modeling of ferroelectrics, both theorists and experimentalists can finally probe the same length and time scales. This allows realtime feedback between theory and experiment, with new discoveries now routinely made both in the laboratory and on the computer. Throughout this chapter, we will highlight the recent advances in density functional theory based modeling and the role it played in our understanding of ultrathin ferroelectrics. We will begin with a brief introduction to ferroelectricity and ferroelectric oxides, followed by an overview of the major theoretical developments. We will then discuss some of the subtleties of ferroelectricity in perovskite oxides, before turning our attention to the main subject of the chapter -- ferroelectricity in ultrathin films. We will discuss in detail the influence of the mechanical, electrical and chemical boundary conditions on the stability of the polar state in a parallel plate capacitor geometry, introducing the notion of depolarization fields that tend to destabilize ferroelectricity. We will look at other ways in which a thin ferroelectric can preserve its polar state, focusing on ferroelectric domains and domain walls. Finally, we will briefly discuss artificially layered ferroelectrics and the potential they hold as tailor-made materials for electronic applications.

Using the metal-insulator transition that takes place as a function of carrier density at the LaAlO$_3$-SrTiO$_3$ interface, oxide diodes have been fabricated with room-temperature breakdown voltages of up to 200 V. With applied voltage, the capacitance of the diodes changes by a factor of 150. The diodes are robust and operate at temperatures up to 270 C.

Epitaxial ultrathin films of the metallic perovskite LaNiO3 were grown on (001) SrTiO3 substrates using off-axis rf magnetron sputtering. The film structure was characterized and their electrical properties investigated. Films thinner than 8 unit cells display a metal-insulator transition at a thickness dependent characteristic temperature. Hall measurements revealed p-type conduction, which was confirmed by electric field-effect experiments. Large changes in the transport properties and the metal-insulator transition temperature were observed for the thinnest LaNiO3 films as the carrier density was electrostatically tuned.

The effects of space charges on hysteresis loops and field distributions in ferroelectrics have been investigated numerically using the phenomenological Landau-Ginzburg-Devonshire theory. Cases with the ferroelectric fully and partially depleted have been considered. In general, increasing the number of charged impurities results in a lowering of the polarization and coercive field values. Squarer loops were observed in the partially depleted cases and a method was proposed to identify fully depleted samples experimentally from dielectric and polarization measurements alone. Unusual field distributions found for higher dopant concentrations have some interesting implications for leakage mechanisms and limit the range of validity of usual semiconductor equations for carrier transport., Comment: 23 pages, 11 figures