Polydomain State Research Articles

Domain Dynamics and Resistive Switching in Ferroelectric Al1–xScxN Thin Film Capacitors

AbstractIn this paper, using a combination of pulse testing measurements and piezoresponse force microscopy (PFM), an investigation of the polarization reversal behavior and the accompanying resistive switching in the Al0.72Sc0.28N thin film capacitors is reported. The obtained results reveal a transition from the nucleation‐limited switching (NLS) in the low field range toward the more uniform switching described by the Kolmogorov–Avrami–Ishibashi (KAI) model in the high field range. It is found that the Al0.72Sc0.28N capacitors exhibit an unusually steep change in the switching time– it decreases by five orders of magnitude with a moderate increase of the applied field. This feature is caused by a significantly higher activation field value (≈126 MV cm−1) in comparison with the conventional perovskite ferroelectrics. PFM visualization of the field‐induced domain dynamics has allowed the evaluation of the nucleation rate and domain wall velocity. Furthermore, capacitors in the polydomain state generated by partial switching of polarization exhibit a significant (up to two orders of magnitude) increase in the steady‐state conductance. This effect is likely caused by the injection of strongly inclined conducting 180° domain walls. Resistance tunability offers additional functionalities to the Al1‐xScxN devices where conductive domain walls are used as active elements.

Schottky Barrier Control of Self-Polarization for a Colossal Ferroelectric Resistive Switching.

Controlling the domain evolution is critical both for optimizing ferroelectric properties and for designing functional electronic devices. Here we report an approach of using the Schottky barrier formed at the metal/ferroelectric interface to tailor the self-polarization states of a model ferroelectric thin film heterostructure system SrRuO3/(Bi,Sm)FeO3. Upon complementary investigations of the piezoresponse force microscopy, electric transport measurements, X-ray photoelectron/absorption spectra, and theoretical studies, we demonstrate that Sm doping changes the concentration and spatial distribution of oxygen vacancies with the tunable host Fermi level which modulates the SrRuO3/(Bi,Sm)FeO3 Schottky barrier and the depolarization field, leading to the evolution of the system from a single domain of downward polarization to polydomain states. Accompanied by such modulation on self-polarization, we further tailor the symmetry of the resistive switching behaviors and achieve a colossal on/off ratio of ∼1.1 × 106 in the corresponding SrRuO3/BiFeO3/Pt ferroelectric diodes (FDs). In addition, the present FD also exhibits a fast operation speed of ∼30 ns with a potential for sub-nanosecond and an ultralow writing current density of ∼132 A/cm2. Our studies provide a way for engineering self-polarization and reveal its strong link to the device performance, facilitating FDs as a competitive memristor candidate used for neuromorphic computing.

Tuning the microstructure, magnetostatic and magnetodynamic properties of highly Al-substituted M-type Sr/Ca hexaferrites prepared by citrate-nitrate auto-combustion method

Double substitution of strontium hexaferrite by calcium and aluminum leads to a tremendous rise of hard magnetic properties, such as coercivity and natural ferromagnetic resonance frequency (NFMR). However, the properties are also inextricably linked to the material microstructure (especially, particle size), to the solid solution inhomogeneity as well as aluminum ions distribution among iron sites in crystal structure. In this work, we obtained M-type hexaferrite particles Sr1-x/12Cax/12Fe12-xAlxO19 (x = 4–6) via a facile citrate-nitrate auto-combustion method and studied the influence of the annealing temperature in a broad range on the microstructure, features of crystal structure and hard magnetic properties. At low annealing temperatures (900–1000°С) hexaferrite nanoparticles with 90% of nominal Al content and a wide chemical distribution are formed. Next, with an increase in the annealing temperature the distribution significantly narrows, chemical composition becomes close to the nominal one and particles size transfer firstly to submicron, then to micron range. The aluminum distribution over iron sites is independent distinctly on the annealing temperature. For all the compositions single domain particles with the maximum coercivity values between 22.8 and 36 kOe are obtained at 1200 °C. At 900–1000 °C the samples demonstrate coercivities up to 25 kOe, while above 1300 °C, the crystallites begin to pass into a polydomain state with a reduced coercivity. The hexaferrites with narrow chemical distribution reveal resonance absorption in sub-terahertz band. The highest NFMR frequency of 270 GHz was observed for x = 5.5 sample annealed at 1400 °C.

Domain wall motion and Barkhausen pulses in lithium niobate with tailored regular 2D domain structure

We present the study of domain structure evolution during polarization reversal in lithium niobate crystal with an initial tailored polydomain state representing a matrix of isolated domains arranged in a square lattice. Domain kinetics during switching differs significantly from the initial single domain state. Growing domains elongate in Y crystallographic direction coinciding with the 2D lattice direction. The field dependence of main domain walls follows the activation law. Typical switching current consists of many Barkhausen pulses separated by low current regions. Korcak’s analysis of switching current has demonstrated the Hurst exponent below 0.5, which indicates an anti-persistent character of the process.

Shape memory behaviors of 3D printed liquid crystal elastomers

As soft active materials, shape-memory polymers (SMPs) and liquid crystal elastomers (LCEs) have attracted considerable research interest due to their potential applications in various areas. SMPs refer to polymeric materials that can return to their permanent shape in response to external stimuli, such as heat, light, and solvent. In this sense, LCEs can exhibit intrinsic shape-memory behaviors since LCEs can switch between two shapes with temperature change due to the order-disorder transition of liquid crystals. In this work, we fabricate both the polydomain and monodomain nematic LCEs through direct ink writing 3D printing. With increasing the temperature of the substrates, the printed LCEs change from the monodomain state to the polydomain state. For polydomain LCEs, a reversible shape change can occur upon constant loading, while the monodomain can switch the shape with temperature in the stress-free state. This two-way shape-memory behavior is caused by the nematic-isotropic phase transition. We further show that the printed LCEs exhibit a good one-way shape-memory effect due to glass transition. The shape recovery region increases with the programming temperature, which is a typical temperature memory effect. Finally, it is demonstrated that complex shape-memory performance can be designed by combining one-way and two-way shape-memory effects. Specifically, for the monodomain LCEs, with increasing temperature, the programmed shape first recovers, and a second shape change can further occur due to the nematic-isotropic transition.

Programming Orientation in Liquid Crystalline Elastomers Prepared with Intra-Mesogenic Supramolecular Bonds.

The large, directional stimuli-response of aligned liquid crystalline elastomers (LCEs) could enable functional utility in robotics, medicine, consumer goods, and photonics. The alignment of LCEs has historically been realized via mechanical alignment of a two-stage reaction. Recent reports widely utilize chain extension reactions of liquid crystal monomers (LCM) to form LCEs that are subject to either surface-enforced or mechanical alignment. Here, we prepare LCEs that contain intra-mesogenic supramolecular bonds synthesized via direct free-radical chain transfer photopolymerization processible by a distinctive mechanical alignment mechanism. The LCEs were prepared by the polymerization of a benzoic acid monomer (11OBA), which dimerized to form a liquid crystal monomer, with a diacrylate LCM (C6M). The incorporation of the intra-mesogenic hydrogen bonds increases the achievable nematic order from mechanical programming. Accordingly, LCEs prepared with larger 11OBA concentration exhibit higher magnitude thermomechanical strain values when compared to a LCE containing only covalent bonds. These LCEs can be reprogrammed with heat to return the aligned film to the polydomain state. The LCE can then be subsequently programmed to orient in a different direction. The facile preparation of (re)programmable LCEs with supramolecular bonds opens new avenues for the implementation of these materials as shape deployable elements.

Bidirectional mechanical switching window in ferroelectric thin films predicted by first-principle-based simulations

Mechanical control of ferroelectric domain evolution has attracted much interest over the past decade. Nevertheless, bidirectional 180° mechanical switching, i.e., a complete cycle of mechanical writing and then erasing of a ferroelectric nanodomain, has not yet been realized in tip-film architectures. Here, via first-principles-based molecular dynamics simulations, we demonstrate that bidirectional 180° mechanical switching is possible in tip-film architectures when screening condition of ferroelectric films and tip loading force are within an appropriate window. The switching utilizes a delicate competition between the flexoelectric field and an overlooked effective dipolar field. The effective dipolar field dominates at small tip force and trigger switching from a downward single-domain state to an upward poly-domain state, whereas the flexoelectric field dominates at relatively large tip force and enables a back-switching. Bidirectional mechanical switching is achieved by applying tip force pulses with alternatively varying strength. The dipole-dipole interaction dynamics play important roles in mechanical switching.

Observability of negative capacitance of a ferroelectric film: Theoretical predictions

We theoretically explore mechanisms that can potentially give rise to the steady-state and transient negative capacitance in a uniaxial ferroelectric film stabilized by a dielectric layer. The analytical expressions for the steady-state capacitance of a single-domain and polydomain states are derived within the Landau-Ginzburg-Devonshire approach and used to study the state stability vs the domain splitting as a function of dielectric layer thickness. Analytical expressions for the critical thickness of the dielectric layer, polarization amplitude, equilibrium domain period, and susceptibility are obtained and corroborated by finite element modeling. We further explore the possible effects of nonlinear screening by two types of screening charges at the ferroelectric-dielectric interface and show that if at least one of the screening charges is very slow, the total polarization dynamics can exhibit complex time- and voltage-dependent behaviors that can be interpreted as an observable negative capacitance. In this setting, the transient negative capacitance effect is accompanied by almost zero dielectric susceptibility in a wide voltage range and low frequencies. These results may help to elucidate the observation of the transient negative capacitance in thin ferroelectric films, and identify materials systems that can give rise to the behavior.

Flexoelectric-effect-based light waveguide liquid crystal display for transparent display

We report a light waveguide liquid crystal display (LCD) based on the flexoelectric effect. The display consists of two parallel flat substrates with a layer of flexoelectric liquid crystal sandwiched between them. A light-emitting diode (LED) is installed on the edge of the display and the produced light is coupled into the display. When no voltage is applied, the liquid crystal is uniformly aligned and is transparent. The incident light propagates through the display by total internal reflection at the interface between the substrate and air, and no light comes out of the viewing side of the display. The display appears transparent. When a voltage is applied, the liquid crystal is switched to a micrometer-sized polydomain state due to flexoelectric interaction and becomes scattering. The incident light is deflected from the waveguide mode and comes out of the viewing side of the display. We achieved thin-film-transistor active matrix compatible driving voltage by doping liquid crystal dimers with large flexoelectric coefficients. The light waveguide LCD does not use polarizers as in conventional LCDs. It has an ultrahigh transmittance near 90% in the voltage-off state. It is very suitable for transparent display, which can be used for head-up display and augmented reality display.

Whither Steady-State Negative Capacitance of a Ferroelectric Film?

We theoretically explore mechanisms that can potentially give rise to steady-state negative capacitance in a uniaxial ferroelectric film stabilized by a dielectric layer. The analytical expressions for the steady-state capacitance of a single-domain state are derived within Landau-Ginzburg-Devonshire approach and used to study the state stability vs. the domain splitting as a function of dielectric layer thickness. Analytical expressions for the critical thickness of the dielectric layer, polarization amplitude, equilibrium domain period and susceptibility are obtained and corroborated by finite element modelling. In the absence of screening charges neither single-domain, nor poly-domain states can exhibit globally-detectable steady-state negative capacitance. We further explore the possible effects of nonlinear screening at the ferroelectric-dielectric interface and show that if at least one of the screening charges is very slow, the total polarization dynamics can exhibit complex time- and voltage dependent behaviors that can be interpreted as a negative capacitance. In this setting, the negative capacitance effect is accompanied by almost zero dielectric susceptibility in a wide voltage range and low frequencies. These results may help to elucidate the fundamental dispute about the possible origin of the quasi-steady-state negative capacitance in thin ferroelectric films, and identify materials systems that can give rise to this behavior.

In situ transport characterization of magnetic states in Nb/Co superconductor/ferromagnet heterostructures.

Employment of the non-trivial proximity effect in superconductor/ferromagnet (S/F) heterostructures for the creation of novel superconducting devices requires accurate control of magnetic states in complex thin-film multilayers. In this work, we study experimentally in-plane transport properties of microstructured Nb/Co multilayers. We apply various transport characterization techniques, including magnetoresistance, Hall effect, and the first-order-reversal-curves (FORC) analysis. We demonstrate how FORC can be used for detailed in situ characterization of magnetic states. It reveals that upon reduction of the external field, the magnetization in ferromagnetic layers first rotates in a coherent scissor-like manner, then switches abruptly into the antiparallel state and after that splits into the polydomain state, which gradually turns into the opposite parallel state. The polydomain state is manifested by a profound enhancement of resistance caused by a flux-flow phenomenon, triggered by domain stray fields. The scissor state represents the noncollinear magnetic state in which the unconventional odd-frequency spin-triplet order parameter should appear. The non-hysteretic nature of this state allows for reversible tuning of the magnetic orientation. Thus, we identify the range of parameters and the procedure for in situ control of devices based on S/F heterostructures.

Mesoscopic structure of mixed type domain walls in multiaxial ferroelectrics

The structure of 180-degree uncharged rotational domain wall in a multiaxial ferroelectric film is studied within the framework of analytical Landau-Ginzburg-Devonshire (LGD) approach. The Finite Element Modelling (FEM) is used to solve numerically the system of the coupled nonlinear Euler-Lagrange (EL) differential equations of the second order for two components of polarization. We show that the structure of the domain wall and corresponding (meta)stable phase of the film are controlled by a single master parameter, dimensionless ferroelectric anisotropy {\mu}. We fitted the static profile of a solitary domain wall, calculated by FEM, with hyperbolic functions for polarization components, and extracted the five {\mu}-dependent parameters from the fitting to FEM curves. The high accuracy of the fitting results allows us to conclude that the analytical functions can be treated as the high-accuracy variational solution of the static EL equations with cubic nonlinearity. We further derive the two-component analytical solutions of the static EL equations for a polydomain 180-degree domain structure in a multiaxial ferroelectric film. The analysis of the free energy dependence on the film thickness and boundary conditions at its surfaces allows to select the domain states corresponding to the minimal energy. The single-domain state is ground for zero polarization derivative at the surfaces, while the poly-domain states minimize the system energy for zero polarization at the surfaces. Counterintuitively, the energy of the polydomain states split into two levels 0 and 1 for zero polarization at the surfaces, and each of the levels is the infinite set of the close-energy sub-levels, which morphology is characterized by different structure of the two-component polarization nodes.

Low-Voltage Domain-Wall LiNbO3 Memristors.

Application of conducting ferroelectric domain walls (DWs) as functional elements may facilitate development of conceptually new resistive switching devices. In a conventional approach, several orders of magnitude change in resistance can be achieved by controlling the DW density using supercoercive voltage. However, a deleterious characteristic of this approach is high-energy cost of polarization reversal due to high leakage current. Here, we demonstrate a new approach based on tuning the conductivity of DWs themselves rather than on domain rearrangement. Using LiNbO3 capacitors with graphene, we show that resistance of a device set to a polydomain state can be continuously tuned by application of subcoercive voltage. The tuning mechanism is based on the reversible transition between the conducting and insulating states of DWs. The developed approach allows an energy-efficient control of resistance without the need for domain structure modification. The developed memristive devices are promising for multilevel memories and neuromorphic computing applications.

Crystallographic orientation-dependent piezoelectric response in BaTiO3 thin films and the domain evolution under different temperatures

The effects of crystallographic orientation on the domain structures and piezoelectric response of BaTiO3 (BTO) thin films were investigated by piezoresponse force microscopy (PFM) systematically. It is found that the domain structures of BTO films are obviously orientation dependent, and the (111) oriented BTO film shows the best piezoelectric properties. Therefore, the nanoscale polydomain switchings within valid single grains of the BTO(111) thin film were observed by PFM under different temperatures. According to the switching process, the a1/a2c, r/a2c, and a1c/r polydomain states were specially introduced into the theoretical model to describe the temperature-induced polydomain switchings of the BTO(111) thin film. The misfit strain-temperature phase diagram was simulated to present the a1/a2c-r/a2c-a1c/r-p domain switching, which corresponds with the threshold temperature of domain switchings obtained from the experimental results of the BTO(111) thin film.

Understanding the Role of Ferroelastic Domains on the Pyroelectric and Electrocaloric Effects in Ferroelectric Thin Films.

Temperature- and electric-field-induced structural transitions in a polydomain ferroelectric can have profound effects on its electrothermal susceptibilities. Here, the role of such ferroelastic domains on the pyroelectric and electrocaloric response is experimentally investigated in thin films of the tetragonal ferroelectric PbZr0.2 Ti0.8 O3 . By utilizing epitaxial strain, a rich set of ferroelastic polydomain states spanning a broad thermodynamic phase space are stabilized. Using temperature-dependent scanning-probe microscopy, X-ray diffraction, and high-frequency phase-sensitive pyroelectric measurements, the propensity of domains to reconfigure under a temperature perturbation is quantitatively studied. In turn, the "extrinsic" contributions to pyroelectricity exclusively due to changes between the ferroelastic domain population is elucidated as a function of epitaxial strain. Further, using highly sensitive thin-film resistive thermometry, direct electrocaloric temperature changes are measured on these polydomain thin films for the first time. The results demonstrate that temperature- and electric-field-driven domain interconversion under compressive strain diminish both the pyroelectric and the electrocaloric effects, while both these susceptibilities are enhanced due to the exact-opposite effect from the extrinsic contributions under tensile strain.

Analytical description of domain morphology and phase diagrams of ferroelectric nanoparticles

Analytical description of domain structure morphology and phase diagrams of ferroelectric nanoparticles is developed in the framework of Landau-Ginzburg-Devonshire approach. To model realistic conditions of incomplete screening of spontaneous polarization at the particle surface, it was considered covered by an ultra-thin layer of screening charge with effective screening length. The phase diagrams, calculated for spherical Sn2P2S6 nanoparticles in coordinates "temperature" and "effective screening length" by finite element modelling, demonstrate the emergence of poly-domain region at the tricritical point and its broadening with increasing the screening length for the particle radius over a critical value. Metastable and stable labyrinthine domain structures exist in Sn2P2S6 nanoparticles with radius (8–10) nm and more. We derived simple analytical expressions for the boundaries between paraelectric, single-domain and poly-domain ferroelectric phases, tricritical point and the necessary condition for the appearance of labyrinthine domains, and demonstrated their high accuracy in comparison with finite element modelling results.Analytical expressions for the dependence of the ferroelectric-paraelectric transition temperature on the particle radius in the single-domain and poly-domain states of the particle were compared with analogous dependences experimentally measured for SrBi2Ta2O9 nanoparticles and simulated for Sn2P2S6 nanocrystals by Monte Carlo method within the framework of axial next-nearest-neighbours Ising model. The analytical expression for the ferroelectric-paraelectric transition temperature in the poly-domain state quantitatively agrees with experimental and simulated results, and it accurately reproduces empirical Ishikawa equation at all temperatures, justifying it theoretically. Analytical description shows that phase diagrams and domain morphologies, which are qualitatively similar to the ones calculated in this work, can be expected in other ferroelectric nanoparticles covered by the screening charges, being rather different for the ferroelectrics with the first and second order ferroelectric-paraelectric transitions respectively.

Reprogrammable, Reprocessible, and Self-Healable Liquid Crystal Elastomer with Exchangeable Disulfide Bonds.

A liquid crystal elastomer (LCE) can be regarded as an integration of mesogenic molecules into a polymer network. The LCE can generate large mechanical actuation when subjected to various external stimuli. Recently, it has been extensively explored to make artificial muscle and multifunctional devices. However, in the commonly adopted two-step crosslinking method for synthesizing monodomain LCEs, the LCE needs to be well-cross-linked in the first step before stretching, which increases the disorder of mesogenic molecules in the final state of the LCE and makes it very challenging to fabricate the LCE of complex shapes. In this article, we developed a new LCE with disulfide bonds, which can be reprogrammed from the polydomain state to the monodomain state either through heating or UV illumination, owing to the rearrangement of the polymer network induced by the metathesis reaction of disulfide bonds. In addition, the newly developed LCE can be easily reprocessed and self-healed by heating. Because of the excellent reprogrammability as well as reprocessability of the LCE, we further fabricated LCE-based active micropillar arrays through robust imprint lithography, which can be hardly achieved using the LCE prepared previously. Finally, we showed an excellent long-term durability of the newly developed LCE.

Effects of annealing atmosphere on microstructure, electrical properties and domain structure of BiFeO3 thin films

Bismuth ferrite thin films were prepared by sol–gel method and spin-coating technique. The effects of annealing atmosphere (air and oxygen) on the microstructure, dielectric, ferroelectric properties and domain structure of bismuth ferrite thin films have been studied systematically. The XRD and AFM results indicate that the bismuth ferrite thin films annealed in air and oxygen atmosphere are rhombohedral perovskite structure and bismuth ferrite thin films annealed in oxygen atmosphere have higher purity, better thickness uniformity and smoothness, and slightly larger grain size than that of the sample annealed in air. Bismuth ferrite annealed in oxygen atmosphere have higher dielectric constant, lower dielectric loss and much higher remnant polarization than that of the thin films annealed in air. The PFM (Piezoelectric Force Microscopy) results indicate that there are coexistence of single domain and polydomain state grains in bismuth ferrite annealed in air and oxygen atmosphere, and the single domain critical size is 80–100 and 100–110 nm respectively. Moreover, there are non-neutral domain wall (negatively charged “tail to tail” and positively charged “head to head” domain wall) in bismuth ferrite thin films annealed in air and oxygen atmosphere.

Viscoelasticity of the polydomain-monodomain transition in main-chain liquid crystal elastomers

Abstract The goal of this study was to explore the rate-dependent behavior of the stretch-induced polydomain-monodomain (PM) transition of a liquid crystal elastomer (LCE). The main-chain LCE was synthesized and then cross-linked in the nematic polydomain state. The PM transition caused a soft-elastic behavior, which was measured using uniaxial tensile tests at multiple strain rates and temperatures. The main finding was that we were able to apply the temperature-dependent shift factor determined for the small strain behavior and in the frequency domain to create master curves for the large-strain response in the strain rate domain. The soft elasticity phenomenon was absent from the stress-strain curve at equilibrium. The results also suggest that the relaxation mechanisms of the network, and not of the mesogen orientation, dominate the rate-dependent behavior. Finally, we observed a relatively slow recovery behavior, suggesting the presence of an additional slow relaxation mechanism.

Investigation of nanoscale domain switching of 0.94 Na0.5 Bi0.5TiO3-0.06 BaTiO3 thin film under different temperatures by piezoresponse force microscopy

The nanoscale domain switching behavior of 0.94 Na0.5 Bi0.5TiO3-0.06 BaTiO3 (NBT-BT6) thin film under different temperatures (25°C-225°C) is investigated by piezoresponse force microscopy (PFM) via the direct observation on their domain structure. The results show that the polycrystal structure with polydomain state is detected in NBT-BT6 thin film. With the temperature increasing, 90°domain switching is observed, however some domains near the grain boundary does not change. The domain switching is attributed to the residual stress induced by the grain deformation, and the grain boundary plays an active role in pinning a preferential polarization state.