Ferroelectric control of magnetic anisotropy

We demonstrate unambiguous evidence of the electric field control of magnetic anisotropy in a wedge-shaped Co film of varying thickness. A copolymer ferroelectric of 70% vinylidene fluoride with 30% trifluoroethylene, P(VDF-TrFE) overlays the Co wedge, providing a large switchable electric field. As the ferroelectric polarization is switched from up to down, the magnetic anisotropy of the Co films changes by as much as 50%. At the lowest Co thickness the magnetic anisotropy switches from out-of-plane to in-plane as the ferroelectric polarization changes from up to down, enabling us to rotate the magnetization through a large angle at constant magnetic field merely by switching the ferroelectric polarization. The large mismatch in the stiffness coefficients between the polymer ferroelectric and metallic ferromagnet excludes typical magnetoelectric strain coupling; rather, the magnetic changes arise from the large electric field at the ferroelectric/ferromagnet interface.     

Ferroelectric BaTiO3 thin films on Ti substrate fabricated using pulsed-laser deposition

We report on the fabrication of ferroelectric BaTiO3 thin films on titanium substrates using pulsed laser deposition and their microstructures and properties. Electron microscopy studies reveal that BaTiO3 films are composed of crystalline assemblage of nanopillars with average cross sections from 100 nm to 200 nm. The BaTiO3 films have good interface structures and strong adhesion with respect to Ti substrates by forming a rutile TiO2 intermediate layer with a gradient microstructure. The room temperature ferroelectric polarization measurements show that the as-deposited BTO films possess nearly the same spontaneous polarization as the bulk BTO ceramics indicating formation of ferroelectric domains in the films. Successful fabrication of such ferroelectric films on Ti has significant importance for the development of new applications such as structural health monitoring spanning from aerospace to civil infrastructure. The work can be extended to integrate other ferroelectric oxide films with various promising properties to monitor the structural health of materials.     

Characterization of ferroelectric/metal interface under the repeated polarization switching

Polarization fatigue mechanism in organic ferroelectrics, structures at interface between ferroelectric vinylidene fluoride oligomer and Al electrode under the repeated polarization switching process were investigated by high-resolution X-ray diffraction (XRD) and Fourier transform infrared spectroscopy (FT-IR). Al₂O₃ layer at interface was formed with increasing the number of polarization reversal. The formation of oxide layer will be strongly related to polarization reversal, thus the repeated charge and discharge process by polarization reversal may promote the oxidation of Al electrode. Furthermore, the structural and orientation changes in ferroelectric molecular films by applying the electric field were observed. The formation of Al₂O₃ layer, as well as the structural changes in thin films, is affected to polarization fatigue process of ferroelectric organic devices.     

Electrostatic coupling and local structural distortions at interfaces in ferroelectric/paraelectric superlattices

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.     

Unexpectedly low barrier of ferroelectric switching in HfO2 via topological domain walls

Fluorite-structure ferroelectrics — in particular the orthorhombic phase of HfO₂ — are of paramount interest to academia and industry because they show unprecedented scalability down to 1-nm-thick size and are compatible with Si electronics. However, their polarization switching is believed to be limited by the intrinsically high energy barrier of ferroelectric domain wall (DW) motions. Here, by unveiling a new topological class of DWs, we establish an atomic-scale mechanism of polarization switching in orthorhombic HfO₂ that exhibits unexpectedly low energy barriers of DW motion (up to 35-fold lower than given by previous conjectures). These findings demonstrate that the nucleation-and-growth-based mechanism is feasible, challenging the commonly held view that the rapid growth of the oppositely polarized domain is impossible. Building on this insight, we describe a strategy to substantially reduce the coercive fields in HfO₂-based ferroelectric devices. Our work is a crucial step towards understanding the polarization switching of HfO₂, which could provide a means to solve the key problems associated with operation speed and endurance.     

Defect‐Mediated Polarization Switching in Ferroelectrics and Related Materials: From Mesoscopic Mechanisms to Atomistic Control

The plethora of lattice and electronic behaviors in ferroelectric and multiferroic materials and heterostructures opens vistas into novel physical phenomena including magnetoelectric coupling and ferroelectric tunneling. The development of new classes of electronic, energy‐storage, and information‐technology devices depends critically on understanding and controlling field‐induced polarization switching. Polarization reversal is controlled by defects that determine activation energy, critical switching bias, and the selection between thermodynamically equivalent polarization states in multiaxial ferroelectrics. Understanding and controlling defect functionality in ferroelectric materials is as critical to the future of oxide electronics and solid‐state electrochemistry as defects in semiconductors are for semiconductor electronics. Here, recent advances in understanding the defect‐mediated switching mechanisms, enabled by recent advances in electron and scanning probe microscopy, are discussed. The synergy between local probes and structural methods offers a pathway to decipher deterministic polarization switching mechanisms on the level of a single atomically defined defect.     

Spontaneous vortex nanodomain arrays at ferroelectric heterointerfaces

The polarization of the ferroelectric BiFeO(3) sub-jected to different electrical boundary conditions by heterointerfaces is imaged with atomic resolution using a spherical aberration-corrected transmission electron microscope. Unusual triangular-shaped nanodomains are seen, and their role in providing polarization closure is understood through phase-field simulations. Heterointerfaces are key to the performance of ferroelectric devices, and this first observation of spontaneous vortex nanodomain arrays at ferroelectric heterointerfaces reveals properties unlike the surrounding film including mixed Ising-Ne?el domain walls, which will affect switching behavior, and a drastic increase of in-plane polarization. The importance of magnetization closure has long been appreciated in multidomain ferromagnetic systems; imaging this analogous effect with atomic resolution at ferroelectric heterointerfaces provides the ability to see device-relevant interface issues. Extension of this technique to visualize domain dynamics is envisioned.     

Polarization-switching D/A converter

This paper describes a novel digital-to-analog (D/A) conversion technique, which uses the analog quantity polarization as a D/A conversion medium. It can be implemented by CMOS capacitors or by ferroelectric capacitors, which exhibit strong nonlinearity in charge versus voltage behavior. Because a ferroelectric material inherently has spontaneous polarization and generally has a large dielectric constant, the effective capacitance of a ferroelectric capacitor is much larger than that of a CMOS capacitor of the same size. This ensures less influence of bottom-electrode parasitic capacitance on a ferroelectric capacitor. Furthermore, a data converter based on ferroelectric capacitors possesses the potential nonvolatile memory function owing to ferroelectric hysteresis. Along with the architecture proposed for polarization-switching digital-to-analog converter (PDAC), its circuit implementation is introduced. Described is implementation of two 9-bit bipolar PDACs: one is based on CMOS capacitors and the other on off-chip ferroelectric capacitors. Experimental results are presented for the performance of these two prototypes.     

Structural consequences of ferroelectric nanolithography

Domains of remnant polarization can be written into ferroelectrics with nanoscale precision using scanning probe nanolithography techniques such as piezoresponse force microscopy (PFM). Understanding the structural effects accompanying this process has been challenging due to the lack of appropriate structural characterization tools. Synchrotron X-ray nanodiffraction provides images of the domain structure written by PFM into an epitaxial Pb(Zr,Ti)O(3) thin film and simultaneously reveals structural effects arising from the writing process. A coherent scattering simulation including the superposition of the beams simultaneously diffracted by multiple mosaic blocks provides an excellent fit to the observed diffraction patterns. Domains in which the polarization is reversed from the as-grown state have a strain of up to 0.1% representing the piezoelectric response to unscreened surface charges. An additional X-ray microdiffraction study of the photon-energy dependence of the difference in diffracted intensity between opposite polarization states shows that this contrast has a crystallographic origin. The sign and magnitude of the intensity contrast between domains of opposite polarization are consistent with the polarization expected from PFM images and with the writing of domains through the entire thickness of the ferroelectric layer. The strain induced by writing provides a significant additional contribution to the increased free energy of the written domain state with respect to a uniformly polarized state.     

Ferroelectrics as Smart Mechanical Materials

The mechanical properties of materials are insensitive to space inversion, even when they are crystallographically asymmetric. In practice, this means that turning a piezoelectric crystal upside down or switching the polarization of a ferroelectric should not change its mechanical response. Strain gradients, however, introduce an additional source of asymmetry that has mechanical consequences. Using nanoindentation and contact‐resonance force microscopy, this study demonstrates that the mechanical response to indentation of a uniaxial ferroelectric (LiNbO₃) does change when its polarity is switched, and use this mechanical asymmetry both to quantify its flexoelectricity and to mechanically read the sign of its ferroelectric domains.     

The origin of ferroelectricity in magnetoelectric YMnO3

Understanding the ferroelectrocity in magnetic ferroelectric oxides is of both fundamental and technological importance. Here, we identify the nature of the ferroelectric phase transition in the hexagonal manganite, YMnO(3), using a combination of single-crystal X-ray diffraction, thorough structure analysis and first-principles density-functional calculations. The ferroelectric phase is characterized by a buckling of the layered MnO(5) polyhedra, accompanied by displacements of the Y ions, which lead to a net electric polarization. Our calculations show that the mechanism is driven entirely by electrostatic and size effects, rather than the usual changes in chemical bonding associated with ferroelectric phase transitions in perovskite oxides. As a result, the usual indicators of structural instability, such as anomalies in Born effective charges on the active ions, do not hold. In contrast to the chemically stabilized ferroelectrics, this mechanism for ferroelectricity permits the coexistence of magnetism and ferroelectricity, and so suggests an avenue for designing novel magnetic ferroelectrics.     

PZT陶瓷的韧性和温度与相变和极化的关系

研究了ＰＺＴ压电陶瓷铁电相变前后的断裂韧性和强度。分析了极化电场与外应力的相对取向对力学性能的影响。探讨了力学性能与极化层导致的畴转向和显微结构变化之间的关系。结果表明，断裂韧性和强度都随着温度的升高而下降至居里点处的低限值，然后略有回升。由于铁电相的热、弹性各向异性引起的内应力和极化残余应力，以及表面应力等的存在，强度比韧性随温度变化的幅度更陡。     

Direct Probing of Polarization Charge at Nanoscale Level

Ferroelectric materials possess spontaneous polarization that can be used for multiple applications. Owing to a long‐term development of reducing the sizes of devices, the preparation of ferroelectric materials and devices is entering the nanometer‐scale regime. Accordingly, to evaluate the ferroelectricity, there is a need to investigate the polarization charge at the nanoscale. Nonetheless, it is generally accepted that the detection of polarization charges using a conventional conductive atomic force microscopy (CAFM) without a top electrode is not feasible because the nanometer‐scale radius of an atomic force microscopy (AFM) tip yields a very low signal‐to‐noise ratio. However, the detection is unrelated to the radius of an AFM tip and, in fact, a matter of the switched area. In this work, the direct probing of the polarization charge at the nanoscale is demonstrated using the positive‐up‐negative‐down method based on the conventional CAFM approach without additional corrections or circuits to reduce the parasitic capacitance. The polarization charge densities of 73.7 and 119.0 µC cm^?2 are successfully probed in ferroelectric nanocapacitors and thin films, respectively. The obtained results show the feasibility of the evaluation of polarization charge at the nanoscale and provide a new guideline for evaluating the ferroelectricity at the nanoscale.     

小温差情况下温度梯度铁电材料零极化偏移现象的理论验证

采用平均场近似下的横场伊辛模型理论,引入描述铁电畸变的分布函数,同时考虑量子起伏效应,研究了温度梯度铁电材料的极化偏移特性,重点针对小温差情况下温度梯度铁电材料极化偏移消失的实验现象进行了理论验证。研究表明,温度梯度的存在导致了材料内部的极化强度的梯度分布,量子起伏效应对温度梯度铁电材料的性质有十分重要的影响,本工作关于温度梯度铁电材料极化偏移的研究结果与实验研究取得了定性一致的结论。当同时在考虑铁电畸变和量子起伏效应时,小温差情况下温度梯度铁电材料极化偏移消失的实验现象得以验证。     

Tunnel junctions with multiferroic barriers

Multiferroics are singular materials that can exhibit simultaneously electric and magnetic orders. Some are ferroelectric and ferromagnetic and provide the opportunity to encode information in electric polarization and magnetization to obtain four logic states. However, such materials are rare and schemes allowing a simple electrical readout of these states have not been demonstrated in the same device. Here, we show that films of La(0.1)Bi(0.9)MnO(3) (LBMO) are ferromagnetic and ferroelectric, and retain both ferroic properties down to a thickness of 2 nm. We have integrated such ultrathin multiferroic films as barriers in spin-filter-type tunnel junctions that exploit the magnetic and ferroelectric degrees of freedom of LBMO. Whereas ferromagnetism permits read operations reminiscent of magnetic random access memories (MRAM), the electrical switching evokes a ferroelectric RAM write operation. Significantly, our device does not require the destructive ferroelectric readout, and therefore represents an advance over the original four-state memory concept based on multiferroics.     

Self-assembled nanoscale ferroelectrics

Multifunctional ferroelectric materials offer a wide range of useful properties, from switchable polarization that can be applied in memory devices to piezoelectric and pyroelectric properties used in actuators, transducers and thermal sensors. At the nanometer scale, however, material properties are expected to be different from those in bulk. Fundamental problems such as the super-paraelectric limit, the influence of the free surface, and of interfacial and bulk defects on ferroelectric switching, etc., arise when scaling down ferroelectrics to nanometer sizes. In order to study these size effects, fabrication methods of high quality nanoscale ferroelectric crystals have to be developed. The present paper briefly reviews self-patterning and self-assembly fabrication methods, including chemical routes, morphological instability of ultrathin films, microemulsion, and self-assembly lift-off, employed up to the date to fabricate ferroelectric structures with lateral sizes in the range of few tens of nanometers.     

Programmable multiple-level phase modulation that uses ferroelectric liquid-crystal spatial light modulators

We present a novel method of producing arbitrarily valued binary phase-only modulation from a commercially available ferroelectric liquid-crystal spatial light modulator that is used in conjunction with simple polarization components. By cascading of such stages, modulators with four and eight equally spaced phase levels are constructed with 128 × 128 pixels. Near-diffraction-limited performance, when stopped down to 64 × 64 pixels, is reported in producing simple diffraction patterns and when used to generate asymmetric spot arrays in the Fourier plane of a lens.     

Schottky barrier versus surface ferroelectric depolarization at Cu/Pb(Zr,Ti)O3 interfaces

The band bending at Cu/PZT(001) interfaces is investigated by X-ray photoelectron spectroscopy (XPS) for a PZT(001) layer which exhibits initial outwards ferroelectric polarization. Two competitive processes are identified: (a) formation of the Schottky barrier between the ferroelectric and unconnected Cu islands, and (b) coalescence of the Cu islands, realisation of an electrical contact to the ground of the system, inducing the apparent loss of the component of the ferroelectric polarization perpendicular to the sample surface, at least as it manifests in band bending. Three mechanisms are proposed to explain this loss of band bending when a full metal layer connected to ground is formed on the surface: (i) over-compensation of depolarization field in the sub-surface region, (ii) formation of domains with in-plane orientation of the polarization vector and (iii) loss of polarization in the near-surface layers of the ferroelectric due to electrons provided by the metal. These result in a non-monotonous variation of binding energies with the amount of Cu deposited. High resolution transmission electron microscopy and piezoresponse force microscopy confirmed these hypotheses. The XPS data allowed also to derive the surface PZT composition, its evolution with the deposition of copper and the formation of surface compounds.     

Organic non-volatile memories from ferroelectric phase-separated blends

New non-volatile memories are being investigated to keep up with the organic-electronics road map. Ferroelectric polarization is an attractive physical property as the mechanism for non-volatile switching, because the two polarizations can be used as two binary levels. However, in ferroelectric capacitors the read-out of the polarization charge is destructive. The functionality of the targeted memory should be based on resistive switching. In inorganic ferroelectrics conductivity and ferroelectricity cannot be tuned independently. The challenge is to develop a storage medium in which the favourable properties of ferroelectrics such as bistability and non-volatility can be combined with the beneficial properties provided by semiconductors such as conductivity and rectification. Here we present an integrated solution by blending semiconducting and ferroelectric polymers into phase-separated networks. The polarization field of the ferroelectric modulates the injection barrier at the semiconductor-metal contact. The combination of ferroelectric bistability with (semi)conductivity and rectification allows for solution-processed non-volatile memory arrays with a simple cross-bar architecture that can be read out non-destructively. The concept of an electrically tunable injection barrier as presented here is general and can be applied to other electronic devices such as light-emitting diodes with an integrated on/off switch.