Light-controlled molecular resistive switching ferroelectric heterojunction

Molecular ferroelectrics have attained significant advancement as a promising approach towards the development of next-generation non-volatile memory devices. Herein, the semiconducting-ferroelectric heterojunctions which is composed of molecular ferroelectrics (R)-(−)-3-hydroxlyquinuclidinium chloride together with organic charge transfer complex is reported. The molecular ferroelectric domain provides polarization and bistability while organic charge transfer phase allows photo-induced charge generation and transport for photovoltaic effect. By switching the direction of the polarization in the ferroelectric phase, the heterojunction-based devices show non-volatile resistive switching under external electric field and photocurrent/voltage induced by light excitation, stable fatigue properties and long retention time. Overall, the photovoltaic controlled resistive switching provides a new route for all-organic multiphase non-volatile memories.     

Ferroelectric polymer gates for non-volatile field effect control of ferromagnetism in (Ga, Mn)As layers

(Ga, Mn)As and other diluted magnetic semiconductors (DMS) attract a great deal of attention for potential spintronic applications because of the possibility of controlling the magnetic properties via electrical gating. Integration of a ferroelectric gate on the DMS channel adds to the system a non-volatile memory functionality and permits nanopatterning via the polarization domain engineering. This topical review is focused on the multiferroic system, where the ferromagnetism in the (Ga, Mn)As DMS channel is controlled by the non-volatile field effect of the spontaneous polarization. Use of ferroelectric polymer gates in such heterostructures offers a viable alternative to the traditional oxide ferroelectrics generally incompatible with DMS. Here we review the proof-of-concept experiments demonstrating the ferroelectric control of ferromagnetism, analyze the performance issues of the ferroelectric gates and discuss prospects for further development of the ferroelectric/DMS heterostructures toward the multiferroic field effect transistor.     

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.     

Reversible electrical switching of spin polarization in multiferroic tunnel junctions

Spin-polarized transport in ferromagnetic tunnel junctions, characterized by tunnel magnetoresistance, has already been proven to have great potential for application in the field of spintronics and in magnetic random access memories. Until recently, in such a junction the insulating barrier played only a passive role, namely to facilitate electron tunnelling between the ferromagnetic electrodes. However, new possibilities emerged when ferroelectric materials were used for the insulating barrier, as these possess a permanent dielectric polarization switchable between two stable states. Adding to the two different magnetization alignments of the electrode, four non-volatile states are therefore possible in such multiferroic tunnel junctions. Here, we show that owing to the coupling between magnetization and ferroelectric polarization at the interface between the electrode and barrier of a multiferroic tunnel junction, the spin polarization of the tunnelling electrons can be reversibly and remanently inverted by switching the ferroelectric polarization of the barrier. Selecting the spin direction of the tunnelling electrons by short electric pulses in the nanosecond range rather than by an applied magnetic field enables new possibilities for spin control in spintronic devices.     

Structural visualization of polarization fatigue in epitaxial ferroelectric oxide devices

Ferroelectric oxides, such as Pb(Zr,Ti)O(3), are useful for electronic and photonic devices because of their ability to retain two stable polarization states, which can form the basis for memory and logic circuitry. Requirements for long-term operation of practical devices such as non-volatile RAM (random access memory) include consistent polarization switching over many (more than 10(12)) cycles of the applied electric field, which represents a major challenge. As switching is largely controlled by the motion and pinning of domain walls, it is necessary to develop suitable tools that can directly probe the ferroelectric domain structures in operating devices-thin-film structures with electrical contacts. A recently developed synchrotron X-ray microdiffraction technique complements existing microscopic probes, and allows us to visualize directly the evolution of polarization domains in ferroelectric devices, through metal or oxide electrodes, and with submicrometre spatial resolution. The images reveal two regimes of fatigue, depending on the magnitude of the electric field pulses driving the device: a low-field regime in which fatigue can be reversed with higher electric field pulses, and a regime at very high electric fields in which there is a non-reversible crystallographic relaxation of the epitaxial ferroelectric film.     

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.     

Solid-state memories based on ferroelectric tunnel junctions

Ferroic-order parameters are useful as state variables in non-volatile information storage media because they show a hysteretic dependence on their electric or magnetic field. Coupling ferroics with quantum-mechanical tunnelling allows a simple and fast readout of the stored information through the influence of ferroic orders on the tunnel current. For example, data in magnetic random-access memories are stored in the relative alignment of two ferromagnetic electrodes separated by a non-magnetic tunnel barrier, and data readout is accomplished by a tunnel current measurement. However, such devices based on tunnel magnetoresistance typically exhibit OFF/ON ratios of less than 4, and require high powers for write operations (>1?×?10(6)?A?cm(-2)). Here, we report non-volatile memories with OFF/ON ratios as high as 100 and write powers as low as ～1?×?10(4)?A?cm(-2) at room temperature by storing data in the electric polarization direction of a ferroelectric tunnel barrier. The junctions show large, stable, reproducible and reliable tunnel electroresistance, with resistance switching occurring at the coercive voltage of ferroelectric switching. These ferroelectric devices emerge as an alternative to other resistive memories, and have the advantage of not being based on voltage-induced migration of matter at the nanoscale, but on a purely electronic mechanism.     

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.     

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.     

Defect-Enhanced Polarization Switching in the Improper Ferroelectric LuFeO3

Results of switching behavior of the improper ferroelectric LuFeO₃ are presented. Using a model set of films prepared under controlled chemical and growth-rate conditions, it is shown that defects can reduce the quasi-static switching voltage by up to 40% in qualitative agreement with first-principles calculations. Switching studies show that the coercive field has a stronger frequency dispersion for the improper ferroelectrics compared to a proper ferroelectric such as PbTiO₃. It is concluded that the primary structural order parameter controls the switching dynamics of such improper ferroelectrics.     

Switching time of nanowire memory

Cadmium sulfide nanowires of 10-nm diameter, electrodeposited in porous anodic alumina films, exhibit an electronic bistability that can be harnessed for non-volatile memory. The current-voltage characteristics of the wires show two stable conductance states that are well-separated (conductances differ by more than 4 orders of magnitude) and long lived (longevity > 1 year at room temperature). These two states can encode binary bits 0 and 1. Here we report measurements of the switching time to switch from the high- to the low-conductance state. These measurements also shed some light on the physical mechanisms underlying the bistability.     

Multi‐Nonvolatile State Resistive Switching Arising from Ferroelectricity and Oxygen Vacancy Migration

Resistive switching phenomena form the basis of competing memory technologies. Among them, resistive switching, originating from oxygen vacancy migration (OVM), and ferroelectric switching offer two promising approaches. OVM in oxide films/heterostructures can exhibit high/low resistive state via conducting filament forming/deforming, while the resistive switching of ferroelectric tunnel junctions (FTJs) arises from barrier height or width variation while ferroelectric polarization reverses between asymmetric electrodes. Here the authors demonstrate a coexistence of OVM and ferroelectric induced resistive switching in a BaTiO₃ FTJ by comparing BaTiO₃ with SrTiO₃ based tunnel junctions. This coexistence results in two distinguishable loops with multi‐nonvolatile resistive states. The primary loop originates from the ferroelectric switching. The second loop emerges at a voltage close to the SrTiO₃ switching voltage, showing OVM being its origin. BaTiO₃ based devices with controlled oxygen vacancies enable us to combine the benefits of both OVM and ferroelectric tunneling to produce multistate nonvolatile memory devices.     

Flexoelectric rotation of polarization in ferroelectric thin films

Strain engineering enables modification of the properties of thin films using the stress from the substrates on which they are grown. Strain may be relaxed, however, and this can also modify the properties thanks to the coupling between strain gradient and polarization known as flexoelectricity. Here we have studied the strain distribution inside epitaxial films of the archetypal ferroelectric PbTiO(3), where the mismatch with the substrate is relaxed through the formation of domains (twins). Synchrotron X-ray diffraction and high-resolution scanning transmission electron microscopy reveal an intricate strain distribution, with gradients in both the vertical and, unexpectedly, the horizontal direction. These gradients generate a horizontal flexoelectricity that forces the spontaneous polarization to rotate away from the normal. Polar rotations are a characteristic of compositionally engineered morphotropic phase boundary ferroelectrics with high piezoelectricity; flexoelectricity provides an alternative route for generating such rotations in standard ferroelectrics using purely physical means.     

Programmable polymer thin film and non-volatile memory device

Building on the success of organic electronic devices, such as light-emitting diodes and field-effect transistors, procedures for fabricating non-volatile organic memory devices are now being explored. Here, we demonstrate a novel organic memory device fabricated by solution processing. Programmable electrical bistability was observed in a device made from a polystyrene film containing gold nanoparticles and 8-hydroxyquinoline sandwiched between two metal electrodes. The as-prepared device, which is in a low-conductivity state, displays an abrupt transition to a high-conductivity state under an external bias of 2.8 V. These two states differ in conductivity by about four orders of magnitude. Applying a negative bias of 1.8 V causes the device to return to the low-conductivity state. The electronic transition is attributed to the electric-field-induced charge transfer between the gold nanoparticles and 8-hydroxyquinoline. The transition from the low- to the high-conductivity state takes place in nanoseconds, and is non-volatile, indicating that the device may be used for low-cost, high-density memory storage.     

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.     

Resistive Switching Behavior in Ferroelectric Heterostructures

Resistive random‐access memory (RRAM) is a promising candidate for next‐generation nonvolatile random‐access memory protocols. The information storage in RRAM is realized by the resistive switching (RS) effect. The RS behavior of ferroelectric heterostructures is mainly controlled by polarization‐dominated and defect‐dominated mechanisms. Under certain conditions, these two mechanisms can have synergistic effects on RS behavior. Therefore, RS performance can be effectively improved by optimizing ferroelectricity, conductivity, and interfacial structures. Many methods have been studied to improve the RS performance of ferroelectric heterostructures. Typical approaches include doping elements into the ferroelectric layer, controlling the oxygen vacancy concentration and optimizing the thickness of the ferroelectric layer, and constructing an insertion layer at the interface. Here, the mechanism of RS behavior in ferroelectric heterostructures is briefly introduced, and the methods used to improve RS performance in recent years are summarized. Finally, existing problems in this field are identified, and future development trends are highlighted.     

Characterization of integrated heterostructures of SbSI–La0.67Ca0.33MnO3

Heterostructures of ferroelectric antimony sulpho iodide (SbSI) and colossal magnetoresistive La_0.67Ca_0.33MnO₃ (LCMO) have been grown on NdGaO₃ substrates by pulsed laser deposition (PLD) technique. The integrated structure, with SbSI acting as a gate insulator and LCMO as a semiconductor channel, exhibited field effect along with a channel modulation of about 10%. This ferroelectric field effect has been observed at a voltage of only 2 V. The field effect was non-volatile, and very little change was observed in the channel resistance after more than 2 h. Polarization switching tests showed a small polarization loss of about 5% after more than 10⁷ bipolar switching cycles.     

High-resolution studies of domain switching behavior in nanostructured ferroelectric polymers

We have demonstrated an effective electrical control of polarization in the individual crystalline nanomesas of the ferroelectric polymer, poly(vinylidene fluoride)-trifluoroethylene (PVDF-TrFE) and its relation to the polymer structure. The mechanism of polarization reversal has been investigated via sub-10 nm real space imaging of domain pattern evolution under an applied electric field. The domain switching behavior revealed in PVDF-TrFE nanomesas is drastically different from that observed in inorganic solid-state crystalline ferroelectrics. The nanoscale features of the switching process include remote domain nucleation and spatially nonuniform wall velocity. Local switching spectroscopy and domain dynamics studies relate the observed switching features to a random-bond type disorder associated with defects in conformation and molecular packing.     

Fabrication of epitaxial nanostructured ferroelectrics and investigation of their domain structures

Nanostructured ferroelectrics are important objects for studies on ferroelectric size effects as well as for applications to memory devices with ultra-high memory density. In the present article, we introduce several approaches for the synthesis of confined ferroelectrics with sizes in and below the hundreds of nanometer range, including top-down processes like e-beam lithography, self-assembly methods like chemical solution deposition, and growth by pulsed laser deposition using stencil masks. Furthermore, the ferroelectric domain structure of part of these nanostructures is investigated by means of synchrotron X-ray diffraction, and its contribution to the ferroelectric properties is discussed.