The First High-Temperature Supramolecular Radical Ferroics.

Organic radical ferroics such as TEMPO have attracted widespread interest. However, the relatively low Curie temperature of 287 K and melting point of 311 K severely hinder its application potential. Despite extensive interest, high-temperature radical ferroics have not yet been found. Here, taking advantage of chemical design and supramolecular radical chemistry, we designed two high-temperature organic supramolecular radical ferroics [(NH3 -TEMPO)([18]crown-6)](ReO4 ) (1) and [(NH3 -TEMPO)([18]crown-6)](ClO4 ) (2), which can retain ferroelectricity up to 413 K and 450 K, respectively. To our knowledge, they are both the first supramolecular radical ferroics and unprecedented high-temperature radical ferroics, where the supramolecular component is vital for the stabilization of the radical and extending the working temperature window. Both also have paramagnetism, non-interacting spin moments, and excellent piezoelectric and electrostrictive behaviors comparable to that of LiNbO3 .

Topological Defects in Hexagonal Manganites: Inner Structure and Emergent Electrostatics.

Diverse topological defects arise in hexagonal manganites, such as ferroelectric vortices, as well as neutral and charged domain walls. The topological defects are intriguing because their low symmetry enables unusual couplings between structural, charge, and spin degrees of freedom, holding great potential for novel types of functional 2D and 1D systems. Despite the considerable advances in analyzing the different topological defects in hexagonal manganites, the understanding of their key intrinsic properties is still rather limited and disconnected. In particular, a rapidly increasing number of structural variants is reported without clarifying their relation, leading to a zoo of seemingly unrelated topological textures. Here, we combine picometer-precise scanning-transmission-electron microscopy with Landau theory modeling to clarify the inner structure of topological defects in Er1-xZrxMnO3. By performing a comprehensive parametrization of the inner atomic defect structure, we demonstrate that one primary length scale drives the morphology of both vortices and domain walls. Our findings lead to a unifying general picture of this type of structural topological defects. We further derive novel fundamental and universal properties, such as unusual bound-charge distributions and electrostatics at the ferroelectric vortex cores with emergent U(1) symmetry.

Coexistence of Three Ferroic Orders in the Multiferroic Compound [(CH3 )4 N][Mn(N3 )3 ] with Perovskite-Like Structure.

The perovskite azido compound [(CH3 )4 N][Mn(N3 )3 ], which undergoes a first-order phase change at Tt =310 K with an associated magnetic bistability, was revisited in the search for additional ferroic orders. The driving force for such structural transition is multifold and involves a peculiar cooperative rotation of the [MnN6 ] octahedral as well as order/disorder and off-center shifts of the [(CH3 )4 N](+) cations and bridging azide ligands, which also bend and change their coordination mode. According to DFT calculations the latter two give rise to the appearance of electric dipoles in the low-temperature (LT) polymorph, the polarization of which nevertheless cancels out due to their antiparallel alignment in the crystal. The conversion of this antiferroelectric phase to the paraelectric phase could be responsible for the experimental dielectric anomaly detected at 310 K. Additionally, the structural change involves a ferroelastic phase transition, whereby the LT polymorph exhibits an unusual and anisotropic thermal behavior. Hence, [(CH3 )4 N][Mn(N3 )3 ] is a singular material in which three ferroic orders coexist even above room temperature.

Ferroics in Hybrid Organic-Inorganic Perovskites: Fundamentals, Design Strategies, and Implementation.

Hybrid organic-inorganic perovskites (HOIPs) afford highly versatile structure design and lattice dimensionalities; thus, they are actively researched as material platforms for the tailoring of ferroic behaviors. Unlike single-phase organic or inorganic materials, the interlayer coupling between organic and inorganic components in HOIPs allows the modification of strain and symmetry by chirality transfer or lattice distortion, thereby enabling the coexistence of ferroic orders. This review focuses on the principles for engineering one or multiple ferroic orders in HOIPs, and the conditions for achieving multiferroicity and magnetoelectric properties. The prospects of multilevel ferroic modulation, chiral spin textures, and spin orbitronics in HOIPs are also presented.

From Quantum Materials to Microsystems.

The expression "quantum materials" identifies materials whose properties "cannot be described in terms of semiclassical particles and low-level quantum mechanics", i.e., where lattice, charge, spin and orbital degrees of freedom are strongly intertwined. Despite their intriguing and exotic properties, overall, they appear far away from the world of microsystems, i.e., micro-nano integrated devices, including electronic, optical, mechanical and biological components. With reference to ferroics, i.e., functional materials with ferromagnetic and/or ferroelectric order, possibly coupled to other degrees of freedom (such as lattice deformations and atomic distortions), here we address a fundamental question: "how can we bridge the gap between fundamental academic research focused on quantum materials and microsystems?". Starting from the successful story of semiconductors, the aim of this paper is to design a roadmap towards the development of a novel technology platform for unconventional computing based on ferroic quantum materials. By describing the paradigmatic case of GeTe, the father compound of a new class of materials (ferroelectric Rashba semiconductors), we outline how an efficient integration among academic sectors and with industry, through a research pipeline going from microscopic modeling to device applications, can bring curiosity-driven discoveries to the level of CMOS compatible technology.

Low-energy structural dynamics of ferroelectric domain walls in hexagonal rare-earth manganites.

Domain walls (DWs) in ferroic materials, across which the order parameter abruptly changes its orientation, can host emergent properties that are absent in the bulk domains. Using a broadband (106 to 1010 Hz) scanning impedance microscope, we show that the electrical response of the interlocked antiphase boundaries and ferroelectric DWs in hexagonal rare-earth manganites (h-RMnO3) is dominated by the bound-charge oscillation rather than free-carrier conduction at the DWs. As a measure of the rate of energy dissipation, the effective conductivity of DWs on the (001) surfaces of h-RMnO3 at gigahertz frequencies is drastically higher than that at dc, whereas the effect is absent on surfaces with in-plane polarized domains. First-principles and model calculations indicate that the frequency range and selection rules are consistent with the periodic sliding of the DW around its equilibrium position. This acoustic wave-like mode, which is associated with the synchronized oscillation of local polarization and apical oxygen atoms, is localized perpendicular to the DW but free to propagate along the DW plane. Our results break the ground to understand structural DW dynamics and exploit new interfacial phenomena for novel devices.

A Piezoresponse Force Microscopy Study of CaxBa1-xNb2O6 Single Crystals.

Polar structures of CaxBa1-xNb2O6 (CBN100x) single crystals were investigated using piezoresponse force microscopy. Increasing Ca content results in decreasing domain size and enhancement of the polar disorder. For the composition with x = 0.32 the characteristic domain size is similar to that reported for relaxor Sr0.61Ba0.39Nb2O6 (SBN61). However, decay of an artificial macroscopic domain in CBN32 takes place below the macroscopic transition temperature, contrary to SBN61, where random fields stabilize it above the transition temperature. We can conclude that CBN with 0.26 ≤ x ≤ 0.32 does not display classical relaxor behavior and might be considered as a disordered ferroelectric.

Electric field control of ferromagnetism using multi-ferroics: the bismuth ferrite story.

Since the re-emergence of multi-ferroics and magnetoelectrics almost a decade ago, bismuth ferrite has been among the most heavily studied model system. It is a multi-ferroic with robust ferroelectricity and antiferromagnetism, in conjunction with weak ferromagnetism arising primarily from spin-orbit coupling effects. This material system has generated a significant amount of discussion in the community, because many of the physical properties measured in thin films are different from the bulk. This paper summarizes some of the key observations in this versatile materials system, with a particular focus on thin films, heterostructures and interfacial phenomena.

Control of ferroelectricity and magnetism in multi-ferroic BiFeO3 by epitaxial strain.

Recently, strain engineering has been shown to be a powerful and flexible means of tailoring the properties of ABO3 perovskite thin films. The effect of epitaxial strain on the structure of the perovskite unit cell can induce a host of interesting effects, these arising from either polar cation shifts or rotation of the oxygen octahedra, or both. In the multi-ferroic perovskite bismuth ferrite (BiFeO3-BFO), both degrees of freedom exist, and thus a complex behaviour may be expected as one plays with epitaxial strain. In this paper, we review our results on the role of strain on the ferroic transition temperatures and ferroic order parameters. We find that, while the Néel temperature is almost unchanged by strain, the ferroelectric Curie temperature strongly decreases as strain increases in both the tensile and compressive ranges. Also unexpected is the very weak influence of strain on the ferroelectric polarization value. Using effective Hamiltonian calculations, we show that these peculiar behaviours arise from the competition between antiferrodistortive and polar instabilities. Finally, we present results on the magnetic order: while the cycloidal spin modulation present in the bulk survives in weakly strained films, it is destroyed at large strain and replaced by pseudo-collinear antiferromagnetic ordering. We discuss the origin of this effect and give perspectives for devices based on strain-engineered BiFeO3.