Ferroelectric domain wall memory with embedded selector realized in LiNbO3 single crystals integrated on Si wafers.

Interfacial 'dead' layers between metals and ferroelectric thin films generally induce detrimental effects in nanocapacitors, yet their peculiar properties can prove advantageous in other electronic devices. Here, we show that dead layers with low Li concentration located at the surface of LiNbO3 ferroelectric materials can function as unipolar selectors. LiNbO3 mesa cells were etched from a single-crystal LiNbO3 substrate, and Pt metal contacts were deposited on their sides. Poling induced non-volatile switching of ferroelectric domains in the cell, and volatile switching in the domains in the interfacial (dead) layers, with the domain walls created within the substrate being electrically conductive. These features were also confirmed using single-crystal LiNbO3 thin films bonded to SiO2/Si wafers. The fabricated nanoscale mesa-structured memory cell with an embedded interfacial-layer selector shows a high on-to-off ratio (>106) and high switching endurance (~1010 cycles), showing potential for the fabrication of crossbar arrays of ferroelectric domain wall memories.

Non-Polar and Complementary Resistive Switching Characteristics in Graphene Oxide devices with Gold Nanoparticles: Diverse Approach for Device Fabrication.

Downscaling limitations and limited write/erase cycles in conventional charge-storage based non-volatile memories stimulate the development of emerging memory devices having enhanced performance. Resistive random-access memory (RRAM) devices are recognized as the next-generation memory devices for employment in artificial intelligence and neuromorphic computing, due to their smallest cell size, high write/erase speed and endurance. Unipolar and bipolar resistive switching characteristics in graphene oxide (GO) have been extensively studied in recent years, whereas the study of non-polar and complementary switching is scarce. Here we fabricated GO-based RRAM devices with gold nanoparticles (Au Nps). Diverse types of switching behavior are observed by changing the processing methods and device geometry. Tri-layer GO-based devices illustrated non-polar resistive switching, which is a combination of unipolar and bipolar switching. Five-layer GO-based devices depicted complementary resistive switching having the lowest current values ~12 µA; and this structure is capable of resolving the sneak path issue. Both devices show good retention and endurance performance. Au Nps in tri-layer devices assisted the conducting path, whereas in five-layer devices, Au Nps layer worked as common electrodes between co-joined cells. These GO-based devices with Au Nps comprising different configuration are vital for practical applications of emerging non-volatile resistive memories.

Giant polarization in super-tetragonal thin films through interphase strain.

Strain engineering has emerged as a powerful tool to enhance the performance of known functional materials. Here we demonstrate a general and practical method to obtain super-tetragonality and giant polarization using interphase strain. We use this method to create an out-of-plane-to-in-plane lattice parameter ratio of 1.238 in epitaxial composite thin films of tetragonal lead titanate (PbTiO3), compared to 1.065 in bulk. These thin films with super-tetragonal structure possess a giant remanent polarization, 236.3 microcoulombs per square centimeter, which is almost twice the value of known ferroelectrics. The super-tetragonal phase is stable up to 725°C, compared to the bulk transition temperature of 490°C. The interphase-strain approach could enhance the physical properties of other functional materials.

Temporary formation of highly conducting domain walls for non-destructive read-out of ferroelectric domain-wall resistance switching memories.

Erasable conductive domain walls in insulating ferroelectric thin films can be used for non-destructive electrical read-out of the polarization states in ferroelectric memories. Still, the domain-wall currents extracted by these devices have not yet reached the intensity and stability required to drive read-out circuits operating at high speeds. This study demonstrated non-destructive read-out of digital data stored using specific domain-wall configurations in epitaxial BiFeO3 thin films formed in mesa-geometry structures. Partially switched domains, which enable the formation of conductive walls during the read operation, spontaneously retract when the read voltage is removed, reducing the accumulation of mobile defects at the domain walls and potentially improving the device stability. Three-terminal memory devices produced 14 nA read currents at an operating voltage of 5 V, and operated up to T = 85 °C. The gap length can also be smaller than the film thickness, allowing the realization of ferroelectric memories with device dimensions far below 100 nm.

Nonequilibrium ferroelectric-ferroelastic 10 nm nanodomains: wrinkles, period-doubling, and power-law relaxation.

Since the 1935 work of Landau-Lifshitz and of Kittel in 1946 all ferromagnetic, ferroelectric, and ferroelastic domains have been thought to be straight-sided with domain widths proportional to the square root of the sample thickness. We show in the present work that this is not true. We also discover period doubling domains predicted by Metaxas et al (2008 Phys. Rev. Lett. 99 217208) and modeled by Wang and Zhao (2015 Sci. Rep. 5 8887). We examine non-equilibrium ferroic domain structures in perovskite oxides with respect to folding, wrinkling, and relaxation and suggest that structures are kinetically limited and in the viscous flow regime predicted by Metaxas et al in 2008 but never observed experimentally. Comparisons are made with liquid crystals and hydrodynamic instabilities, including chevrons, and fractional power-law relaxation. As Shin et al (2016 Soft Matter 12 3502) recently emphasized: 'An understanding of how these folds initiate, propagate, and interact with each other is still lacking'. Inside each ferroelastic domain are ferroelectric 90° nano-domains with 10 nm widths and periodicity in agreement with the 10 nm theoretical minima predicted by Feigl et al (2014 Nat. Commun. 5 4677). Evidence is presented for domain-width period doubling, which is common in polymer films but unknown in ferroic domains. A discussion of the folding-to-period doubling phase transition model of Wang and Zhao is included.

Stability of Polar Vortex Lattice in Ferroelectric Superlattices.

A novel mesoscale state comprising of an ordered polar vortex lattice has been demonstrated in ferroelectric superlattices of PbTiO3/SrTiO3. Here, we employ phase-field simulations, analytical theory, and experimental observations to evaluate thermodynamic conditions and geometric length scales that are critical for the formation of such exotic vortex states. We show that the stability of these vortex lattices involves an intimate competition between long-range electrostatic, long-range elastic, and short-range polarization gradient-related interactions leading to both an upper and a lower bound to the length scale at which these states can be observed. We found that the critical length is related to the intrinsic domain wall width, which could serve as a simple intuitive design rule for the discovery of novel ultrafine topological structures in ferroic systems.

Implementing Room-Temperature Multiferroism by Exploiting Hexagonal-Orthorhombic Morphotropic Phase Coexistence in LuFeO3 Thin Films.

Room-temperature multiferroism in LuFeO3 (LFO) films is demonstrated by exploiting the orthorhombic-hexagonal (o-h) morphotrophic phase coexistence. The LFO film further reveals a magnetoelectric coupling effect that is not shown in single-phase (h- or o-) LFO. The observed multiferroism is attributed to the combination of sufficient polarization from h-LFO and net magnetization from o-LFO.

Quantum electric-dipole liquid on a triangular lattice.

Geometric frustration and quantum fluctuations may prohibit the formation of long-range ordering even at the lowest temperature, and therefore liquid-like ground states could be expected. A good example is the quantum spin liquid in frustrated magnets. Geometric frustration and quantum fluctuations can happen beyond magnetic systems. Here we propose that quantum electric-dipole liquids, analogues of quantum spin liquids, could emerge in frustrated dielectrics where antiferroelectrically coupled electric dipoles reside on a triangular lattice. The quantum paraelectric hexaferrite BaFe12O19 with geometric frustration represents a promising candidate for the proposed electric-dipole liquid. We present a series of experimental lines of evidence, including dielectric permittivity, heat capacity and thermal conductivity measured down to 66 mK, to reveal the existence of an unusual liquid-like quantum phase in BaFe12O19, characterized by itinerant low-energy excitations with a small gap. The possible quantum liquids of electric dipoles in frustrated dielectrics open up a fresh playground for fundamental physics.

Spin phonon interactions and magnetodielectric effects in multiferroic BiFeO3-PbTiO3.

Here, we report the observation of magneto-dielectric and magneto-structural coupling in (1 - x)BiFeO3-xPbTiO3 i.e.(1 - x)BF-xPT) solid solutions with compositions in the vicinity of morphotropic phase boundary, as manifested by a combination of temperature dependent magnetic, Raman and dielectric measurements. Whilst x-ray diffraction and Raman spectroscopy suggest absence of any structural phase transition between 90-300 K, temperature dependent magnetic studies reveal magnetic anomalies in the solid solutions. These results are complemented by identical observations in the dielectric measurements at similar temperatures indicating a coupling between magnetic and electric order parameters. Further, Raman studies on rhombohedral i.e. x = 0.20 samples reveal a coupling between the magnetic structure and the lattice, causing spin-phonon interactions that are possibly responsible for observed magneto-dielectric effects. Our results illustrate that the phase transitions in BiFeO3-PbTiO3 system are fewer than expected and are attributed to a spatial averaging in an inhomogeneous albeit single-phase material due to clustering of Fe- or Ti-ions on different length scales.

Enhanced resistive switching in forming-free graphene oxide films embedded with gold nanoparticles deposited by electrophoresis.

Forming-free resistive random access memory (ReRAM) devices having low switching voltages are a prerequisite for their commercial applications. In this study, the forming-free resistive switching characteristics of graphene oxide (GO) films embedded with gold nanoparticles (Au Nps), having an enhanced on/off ratio at very low switching voltages, were investigated for non-volatile memories. The GOAu films were deposited by the electrophoresis method and as-grown films were found to be in the low resistance state; therefore no forming voltage was required to activate the devices for switching. The devices having an enlarged on/off ratio window of ∼10(6) between two resistance states at low voltages (<1 V) for repetitive dc voltage sweeps showed excellent properties of endurance and retention. In these films Au Nps were uniformly dispersed over a large area that provided charge traps, which resulted in improved switching characteristics. Capacitance was also found to increase by a factor of ∼10, when comparing high and low resistance states in GOAu and pristine GO devices. Charge trapping and de-trapping by Au Nps was the mechanism responsible for the improved switching characteristics in the films.

Giant Dielectric Permittivity in Ferroelectric Thin Films: Domain Wall Ping Pong.

The dielectric permittivity in ferroelectric thin films is generally orders of magnitude smaller than in their bulk. Here, we discover a way of increasing dielectric constants in ferroelectric thin films by ca. 500% by synchronizing the pulsed switching fields with the intrinsic switching time (nucleation of domain plus forward growth from cathode to anode). In a 170-nm lead zirconate titanate thin film with an average grain size of 850 nm this produces a dielectric constant of 8200 with the maximum nucleus density of 3.8 µm(-2), which is one to three orders of magnitude higher than in other dielectric thin films. This permits smaller capacitors in memory devices and is a step forward in making ferroelectric domain-engineered nano-electronics.

The nature of magnetoelectric coupling in Pb(Zr,Ti)O3 -Pb(Fe,Ta)O3.

The coupling between magnetization and polarization in a room temperature multiferroic (Pb(Zr,Ti)O3 -Pb(Fe,Ta)O3 ) is explored by monitoring the changes in capacitance that occur when a magnetic field is applied in each of three orthogonal directions. Magnetocapacitance effects, consistent with P(2) M(2) coupling, are strongest when fields are applied in the plane of the single crystal sheet investigated.

Giant Negative Electrocaloric Effect in Antiferroelectric La-Doped Pb(ZrTi)O3 Thin Films Near Room Temperature.

Antiferroelectric thin films are demonstrated as a new class of giant electrocaloric materials that exhibit a negative electrocaloric response of about -5 K near room temperature. The giant negative electrocaloric effect may open up a new paradigm for light, compact, reliable, and high-efficiency refrigeration devices.

Some current problems in perovskite nano-ferroelectrics and multiferroics: kinetically-limited systems of finite lateral size.

We describe some unsolved problems of current interest; these involve quantum critical points in ferroelectrics and problems which are not amenable to the usual density functional theory, nor to classical Landau free energy approaches (they are kinetically limited), nor even to the Landau-Kittel relationship for domain size (they do not satisfy the assumption of infinite lateral diameter) because they are dominated by finite aperiodic boundary conditions.

Exploring vertex interactions in ferroelectric flux-closure domains.

Using piezoresponse force microscopy, we have observed the progressive development of ferroelectric flux-closure domain structures and Landau-Kittel-type domain patterns, in 300 nm thick single-crystal BaTiO3 platelets. As the microstructural development proceeds, the rate of change of the domain configuration is seen to decrease exponentially. Nevertheless, domain wall velocities throughout are commensurate with creep processes in oxide ferroelectrics. Progressive screening of macroscopic destabilizing fields, primarily the surface-related depolarizing field, successfully describes the main features of the observed kinetics. Changes in the separation of domain-wall vertex junctions prompt a consideration that vertex-vertex interactions could be influencing the measured kinetics. However, the expected dynamic signatures associated with direct vertex-vertex interactions are not resolved. If present, our measurements confine the length scale for interaction between vertices to the order of a few hundred nanometers.

Giant room-temperature elastocaloric effect in ferroelectric ultrathin films.

Environmentally friendly ultrathin BaTiO3 capacitors can exhibit a giant stress-induced elastocaloric effect without hysteresis loss or Joule heating. By combining this novel elastocaloric effect with the intrinsic electrocaloric effect, an ideal refrigeration cycle with high performance (temperature change over 10 K with a wide working-temperature window of 60 K) at room temperature is proposed for future cooling applications.

Ferroelectric domain wall injection.

Ferroelectric domain wall injection has been demonstrated by engineering of the local electric field, using focused ion beam milled defects in thin single crystal lamellae of KTiOPO4 (KTP). The electric field distribution (top) displays localized field hot-spots, which correlate with nucleation events (bottom). Designed local field variations can also dictate subsequent domain wall mobility, demonstrating a new paradigm in ferroelectric domain wall control.

Lanthanum Gadolinium Oxide: A New Electronic Device Material for CMOS Logic and Memory Devices.

A comprehensive study on the ternary dielectric, LaGdO3, synthesized and qualified in our laboratory as a novel high-k dielectric material for logic and memory device applications in terms of its excellent features that include a high linear dielectric constant (k) of ~22 and a large energy bandgap of ~5.6 eV, resulting in sufficient electron and hole band offsets of ~2.57 eV and ~1.91 eV, respectively, on silicon, good thermal stability with Si and lower gate leakage current densities within the International Technology Roadmap for Semiconductors (ITRS) specified limits at the sub-nanometer electrical functional thickness level, which are desirable for advanced complementary metal-oxide-semiconductor (CMOS), bipolar (Bi) and BiCMOS chips applications, is presented in this review article.