Integrating epitaxial thin films of ferroelectric PbTiO3 and paraelectric SrTiO3 into artificially layered periodic superlattices provides a unique platform for tuning strain, depolarization, and interfacial/surface energies, thereby accessing a rich phase diagram of topological polar structures (skyrmions, vortices, merons, or sinusoidal waves) and superstructures (polar supercrystals). Here we show that the 3D arrangement of polar vortices in a supercrystal suppresses thermal conductivity (k) of PTO/STO superlattices (SLs). The temperature dependence of k reflects the evolution of the polar superstructure, as determined by X-ray diffraction and transmission electron microscopy. The comparison with other SLs suggests that the 3D arrangement is crucial for controlling thermal conductivity beyond the usual interfacial scattering. Moreover, we observed an unexpected reduction in thermal conductivity with increasing superlattice thickness, a phenomenon reminiscent of phonon-wave Anderson localization. Our results show that complex polar superstructures can be useful active elements for modulating heat transport in technologies where control over heat dissipation is critical.

Here we investigate epitaxial Hf0.5Zr0.5O2 ferroelectric thin films as potential candidates to be used as non-volatile electric-field-modulated thermal memories. The electric-field dependence of the thermal conductivity of metal/Hf0.5Zr0.5O2/Y2O3:ZrO2 devices is found to be hysteretic-resembling a polarization vs. electric field hysteresis loop-, reaching a maximum (minimum) at large applied positive (negative) electric fields from the top metallic electrode. This dynamic thermal response is compatible with the effects of the coupling between the ferroelectric polarization and oxygen ion migration in the Hf0.5Zr0.5O2 layer, in which the oxygen vacancies are the main phonon scattering centers and the polarization acts as an electrically active ion migration barrier that creates the hysteresis. This new mechanism enables two non-volatile states: high (ON) and low (OFF) thermal conductivity states when the electric field is removed, with an ON/OFF ratio of 1.6, which can be switched with applied voltages lower than -5 and +5 V, respectively. Both the ON and OFF states exhibit high stability over time, though the switching speed is limited by ion mobility in the Y2O3:ZrO2 electrode.

Here we investigate epitaxial Hf0.5Zr0.5O2 ferroelectric thin films as potential candidates to be used as non-volatile electric-field-modulated thermal memories. The electric-field dependence of the thermal conductivity of metal/Hf0.5Zr0.5O2/YSZ devices is found to be hysteretic, resembling the polarization vs electric field hysteresis loops, being maximum (minimum) at large applied positive (negative) voltages from the top metallic electrode. This dynamic thermal response is compatible with the coupling between the ferroelectric polarization and the oxygen ion migration, in which the oxygen vacancies are the main phonon scattering sources and the polarization acts as an electrically active ion migration barrier that creates the hysteresis. This new mechanism enables two non-volatile thermal states: high (ON) and low (OFF) thermal conductivity, with an ON/OFF ratio of 1.6. Both the ON and OFF states exhibit high stability over time, though the switching speed is limited by ion mobility in the YSZ electrode.

Abstract Films of ferroelectric hafnia have hitherto been deposited on electrodes with a non‐fluorite crystal structure. As a result, they are polycrystalline, contain fractions of non‐ferroelectric polymorphs or have poor crystal quality. Here, a strategy that circumvents all these limitations is shown. Seven nanometers‐thick epitaxial Hf0.5Zr0.5O2 (HZO) films are deposited directly on yttria‐stabilized zirconia (YSZ) single‐crystals. The fluorite structure of the whole system enables coherent epitaxy, while the substrate orientation induces polymorph‐selective growth, being the HZO films orthorhombic on YSZ(111) and monoclinic on YSZ(001). Besides, the YSZ substrate can play the role of a buried floating electrode under the appropriate measuring conditions (temperature and frequency) thanks to its thermally‐activated oxygen conductivity. Indeed, out‐of‐plane ferroelectric switching is confirmed in the orthorhombic HZO samples at 185 °C and 0.01 Hz frequency. This original approach avoids the need to deposit conducting bottom layers, allowing high‐quality orthorhombic hafnia to be obtained directly on the substrate and its ferroelectric nature to be studied. Moreover, it constitutes a case of ion‐driven ferroelectric switching, and thus gives support to the recently proposed relationship between ionic conductivity, and ferroelectricity in fluorite systems.

Accessing the regime of coherent phonon propagation in nanostructures opens enormous possibilities to control the thermal conductivity in energy harvesting devices, phononic circuits, etc. In this paper we show that coherent phonons contribute substantially to the thermal conductivity of LaCoO3/SrTiO3 oxide superlattices, up to room temperature. We show that their contribution can be tuned through small variations of the superlattice periodicity, without changing the total superlattice thickness. Using this strategy, we tuned the thermal conductivity by 20% at room temperature. We also discuss the role of interface mixing and epitaxial relaxation as an extrinsic, material dependent key parameter for understanding the thermal conductivity of oxide superlattices.

We present a detailed analysis of the temperature dependence of the thermal conductivity of a ferroelectric PbTiO3 thin film deposited in a composition-spread geometry enabling a continuous range of compositions from ∼25% titanium deficient to ∼20% titanium rich to be studied. By fitting the experimental results to the Debye model we deconvolute and quantify the two main phonon-scattering sources in the system: ferroelectric domain walls (DWs) and point defects. Our results prove that ferroelectric DWs are the main agent limiting the thermal conductivity in this system, not only in the stoichiometric region of the thin film ([Pb]/[Ti] ≈ 1) but also when the concentration of the cation point defects is significant (up to ∼15%). Hence, DWs in ferroelectric materials are a source of phonon scattering at least as effective as point defects. Our results demonstrate the viability and effectiveness of using reconfigurable DWs to control the thermal conductivity in solid-state devices.

Flexoelectricity is a property of dielectric materials whereby they exhibit electric polarization induced by strain gradients; while this effect can be negligible at the macroscale, it can become dominant at the nanoscale, where strain gradients can turn out to be tremendous. Previous works have demonstrated that flexoelectricity coupled with piezoelectricity enables the mechanical writing of ferroelectric polarization. When considering ferroelectric materials with out-of-plane polarization, the coupling of piezoelectricity with flexoelectricity can insert a mechanical asymmetry to the system and enable the distinction of oppositely polarized domains, based on their nanomechanical response. Using atomic force microscopy and, more specifically, contact resonance techniques, the coupling of flexoelectricity to piezoelectricity can be exploited to mechanically read the sign of ferroelectric polarization in a non-destructive way. We have measured a variety of ferroelectric materials, from a single crystal to thin films, and domains that are polarized down always appear to be stiffer than oppositely polarized domains. In this article, we demonstrate experimentally that the phenomenon is size-dependent and strongly enhanced when the dimension of the material is reduced to nanoscale in thin films. Ultimately, we demonstrate how the sensitivity in mechanical reading of ferroelectric polarization can be improved by appropriately tuning the mechanical stiffness of the cantilevers.

Accessing the regime of coherent phonon propagation in nanostructures opens enormous possibilities to control the thermal conductivity in energy harvesting devices, phononic circuits, etc. In this paper we show that coherent phonons contribute substantially to the thermal conductivity of LaCoO3/SrTiO3 oxide superlattices, up to room temperature. We show that their contribution can be tuned through small variations of the superlattice periodicity, without changing the total superlattice thickness. Using this strategy, we tuned the thermal conductivity by 20% at room temperature. We also discuss the role of interface mixing and epitaxial relaxation as an extrinsic, material dependent key parameter for understanding the thermal conductivity of oxide superlattices.

SrMnO3 has a rich epitaxial strain-dependent ferroic phase diagram, in which a variety of magnetic orderings, even ferroelectricity, and thus multiferroicity, are accessible by gradually modifying the strain. Different relaxation processes, though, including the presence of strain-induced oxygen vacancies, can severely curtail the possibility of stabilizing these ferroic phases. Here, we report on a thorough investigation of the strain relaxation mechanisms in SrMnO3 films grown on several substrates imposing varying degrees of strain from slightly compressive (−0.39%) to largely tensile ≈+3.8%. First, we determine the strain dependency of the critical thickness (tc) below which pseudomorphic growth is obtained. Second, the mechanisms of stress relaxation are elucidated, revealing that misfit dislocations and stacking faults accommodate the strain above tc. Yet, even for films thicker than tc, the atomic monolayers below tc are proved to remain fully coherent. Therefore, multiferroicity may also emerge even in films that appear to be partially relaxed. Last, we demonstrate that fully coherent films with the same thickness present a lower oxygen content for increasing tensile mismatch with the substrate. This behavior proves the coupling between the formation of oxygen vacancies and epitaxial strain, in agreement with first-principles calculations, enabling the strain control of the Mn3+/Mn4+ ratio, which strongly affects the magnetic and electrical properties. However, the presence of oxygen vacancies/Mn3+ cations reduces the effective epitaxial strain in the SrMnO3 films and, thus, the accessibility to the strain-induced multiferroic phase.

Accessing the regime of coherent phonon propagation in nanostructures opens enormous possibilities to control the thermal conductivity in energy harvesting devices, phononic circuits, etc. In this paper we show that coherent phonons contribute substantially to the thermal conductivity of LaCoO3/SrTiO3 oxide superlattices, up to room temperature. We show that their contribution can be tuned through small variations of the superlattice periodicity, without changing the total superlattice thickness. Using this strategy, we tuned the thermal conductivity by 20 interface mixing and epitaxial relaxation as an extrinsic, material dependent key parameter for understanding the thermal conductivity of oxide superlattices.

Scanning nanobeam electron diffraction (NBED) with fast pixelated detectors is a valuable technique for rapid, spatially resolved mapping of lattice structure over a wide range of length scales. However, intensity variations caused by dynamical diffraction and sample mistilts can hinder the measurement of diffracted disk centers as necessary for quantification. Robust data processing techniques are needed to provide accurate and precise measurements for complex samples and non-ideal conditions. Here we present an approach to address these challenges using a transform, called the exit wave power cepstrum (EWPC), inspired by cepstral analysis in audio signal processing. The EWPC transforms NBED patterns into real-space patterns with sharp peaks corresponding to inter-atomic spacings. We describe a simple analytical model for interpretation of these patterns that cleanly decouples lattice information from the intensity variations in NBED patterns caused by tilt and thickness. By tracking the inter-atomic spacing peaks in EWPC patterns, strain mapping is demonstrated for two practical applications: mapping of ferroelectric domains in epitaxially strained PbTiO3 films and mapping of strain profiles in arbitrarily oriented core-shell Pt-Co nanoparticle fuel-cell catalysts. The EWPC transform enables lattice structure measurement at sub-pm precision and sub-nm resolution that is robust to small sample mistilts and random orientations.

We study the interplay between epitaxial strain, film thickness, and electric field in the creation, modification, and design of distinct ferroelastic structures in PbTiO3 thin films. Strain and thickness greatly affect the structures formed, providing a two-variable parameterization of the resulting self-assembly. Under applied electric fields, these strain-engineered ferroelastic structures are highly malleable, especially when a/c and a(1)/a(2) superdomains coexist. To reconfigure the ferroelastic structures and achieve self-assembled nanoscale-ordered morphologies, pure ferroelectric switching of individual c-domains within the a/c superdomains is essential. The stability, however, of the electrically written ferroelastic structures is in most cases ephemeral; the speed of the relaxation process depends sensitively on strain and thickness. Only under low tensile strain-as is the case for PbTiO3 on GdScO3-and below a critical thickness do the electrically created a/c superdomain structures become stable for days or longer, making them relevant for reconfigurable nanoscale electronics or nonvolatile electromechanical applications.

Domain walls separating regions of opposite polarity in ferroelectric materials are mechanically softer than the domains they separate, a result that extends the distinct physics of domain walls to their mechanical properties.

Domain walls are functionally different from the domains they separate, but little is known about their mechanical properties. Using scanning probe microscopy, we have measured the mechanical response of ferroelectric 180o domain walls and observed that, despite separating domains that are mechanically identical (non-ferroelastic), the walls are mechanically distinct -- softer -- compared to the domains. This effect has been observed in different ferroelectric materials (LiNbO3, BaTiO3, PbTiO3) and with different morphologies (from single crystals to thin films) so it appears to be universal. We propose a theoretical framework that explains the domain wall softening and justifies that the effect should be common to all ferroelectrics.

Achieving efficient spatial modulation of phonon transmission is an essential step on the path to phononic circuits using "phonon currents". With their intrinsic and reconfigurable interfaces, domain walls (DWs), ferroelectrics are alluring candidates to be harnessed as dynamic heat modulators. This paper reports the thermal conductivity of single-crystal PbTiO3 thin films over a wide variety of epitaxial-strain-engineered ferroelectric domain configurations. The phonon transport is proved to be strongly affected by the density and type of DWs, achieving a 61% reduction of the room-temperature thermal conductivity compared to the single-domain scenario. The thermal resistance across the ferroelectric DWs is obtained, revealing a very high value (≈5.0 × 10-9 K m2 W-1), comparable to grain boundaries in oxides, explaining the strong modulation of the thermal conductivity in PbTiO3. This low thermal conductance of the DWs is ascribed to the structural mismatch and polarization gradient found between the different types of domains in the PbTiO3 films, resulting in a structural inhomogeneity that extends several unit cells around the DWs. These findings demonstrate the potential of ferroelectric DWs as efficient regulators of heat flow in one single material, overcoming the complexity of multilayers systems and the uncontrolled distribution of grain boundaries, paving the way for applications in phononics.

Chemical doping and epitaxy can be used to tailor the magnetoelectric properties of multiferroic thin films, such as SrMnO3. Here, we study the dependence of the magnetic order temperatures of Sr1−xBaxMnO3 thin films on epitaxial strain and Ba content. Combining low-energy muon spin spectroscopy and scanning transmission electron microscopy, the broadness of the magnetic transition is attributed to the presence of a Mn-O-Mn angle gradient along the out-of-plane direction. We also demonstrate that the unit cell volume is the key parameter to determine the Néel temperature in Sr1−xBaxMnO3 thin films showing G-type antiferromagnetic order. The occurrence of a simultaneously ferroelectric and ferromagnetic ground state at high strain levels is suggested for the Sr0.8Ba0.2MnO3 thin film deposited on TbScO3.

Ferroelectricity was recently reported in thin films with several compositions in the HfO2-ZrO2 system with orthorhombic crystal structure. In the present paper we study the growth by pulsed laser deposition and the structural characterization of strained epitaxial Hf0.5Zr0.5O2 films on (001)-oriented yttria-stabilized zirconia (YSZ) substrates. We have determined the conditions for the coherent growth and correlated the deposition parameters with the films structure andmicrostructure studied through a combination of x-ray diffraction, electron backscatter diffraction, and scanning transmission electron microscopy. In the range of experimental parameters explored, all the films show monoclinic structure with distorted lattice parameters relative to bulk.

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Journal Article Probing Strain-Induced Phenomena in Low Dimensionality Multiferroic Oxides Get access C Magen, C Magen Laboratorio de Microscopias Avanzadas (LMA), Instituto de Nanociencia de Aragon (INA), Univ. de Zaragoza, Zaragoza, Spain Search for other works by this author on: Oxford Academic Google Scholar R Guzman, R Guzman Laboratorio de Microscopias Avanzadas (LMA), Instituto de Nanociencia de Aragon (INA), Univ. de Zaragoza, Zaragoza, SpainInstitut de Ciencia de Materials de Barcelona, ICMAB-CSIC, Barcelona, Spain Search for other works by this author on: Oxford Academic Google Scholar S Farokhipoor, S Farokhipoor Zernike Institute for Advanced Materials, Univ. of Groningen, AG Groningen, NetherlandsDepartment of Materials Science & Metallurgy, Univ. of Cambridge, UK Search for other works by this author on: Oxford Academic Google Scholar L Maurel, L Maurel Instituto de Nanociencia de Aragon (INA), Univ. de Zaragoza, Zaragoza, Spain Search for other works by this author on: Oxford Academic Google Scholar E Langenberg, E Langenberg Instituto de Nanociencia de Aragon (INA), Univ. de Zaragoza, Zaragoza, SpainInstituto de Ciencia de Materiales de Aragon, Univ. de Zaragoza-CSIC, Zaragoza, Spain Search for other works by this author on: Oxford Academic Google Scholar J Iniguez, J Iniguez Institut de Ciencia de Materials de Barcelona, ICMAB-CSIC, Barcelona, SpainLuxembourg Institute of Science and Technology (LIST), Esch/Alzette, Luxembourg Search for other works by this author on: Oxford Academic Google Scholar S Venkatesan, S Venkatesan Ludwig-Maximilians-Universitat Munchen, Munich, Germany Search for other works by this author on: Oxford Academic Google Scholar Andrew R Lupini, Andrew R Lupini Materials Science and Technology Division, Oak Ridge National Laboratory, Tennessee, US Search for other works by this author on: Oxford Academic Google Scholar E Snoeck, E Snoeck CEMES - CNRS, Toulouse, France Search for other works by this author on: Oxford Academic Google Scholar M Mostovoy, M Mostovoy Zernike Institute for Advanced Materials, Univ. of Groningen, AG Groningen, Netherlands Search for other works by this author on: Oxford Academic Google Scholar ... Show more P A Algarabel, P A Algarabel Instituto de Ciencia de Materiales de Aragon, Univ. de Zaragoza-CSIC, Zaragoza, Spain Search for other works by this author on: Oxford Academic Google Scholar J A Pardo, J A Pardo Laboratorio de Microscopias Avanzadas (LMA), Instituto de Nanociencia de Aragon (INA), Univ. de Zaragoza, Zaragoza, Spain Search for other works by this author on: Oxford Academic Google Scholar B Noheda B Noheda Zernike Institute for Advanced Materials, Univ. of Groningen, AG Groningen, Netherlands Search for other works by this author on: Oxford Academic Google Scholar Microscopy and Microanalysis, Volume 23, Issue S1, 1 July 2017, Pages 1726–1727, https://doi.org/10.1017/S1431927617009291 Published: 04 August 2017