Monodomain State Research Articles

Giant enhancement and quick stabilization of capacitance in antiferroelectrics by phase transition engineering

The antiferroelectric-ferroelectric phase transition is a basic principle that holds promise for antiferroelectric ceramics in high capacitance density nonlinear capacitors. So far, the property optimization based on antiferroelectric-ferroelectric transition is solely undertaken by chemical composition tailoring. Alternately, here we propose a phase transition engineering tactic by applying pulsed electric stimulus near the critical electric field, which finally results in ~54.3% enhancement and quick stabilization of capacitance density in Pb0.97La0.02(Zr0.35Sn0.55Ti0.10)O3 antiferroelectric ceramics. Ex-situ and in-situ structural characterizations show that electric stimuli can induce the charming successive structural evolution, including domain evolution from multidomain to monodomain state, and modulation period change from 7.49 to 7.73. Structure-property correlation indicates that the antiferroelectric-ferroelectric phase transition engineering mainly stems from the unexpected irreversible recovery of the modulated structures. The present findings would deepen the understanding of the structural phase transition and provoke composition-independent post-treatment property innovation in the incommensurate antiferroelectric materials and devices.

4D printing of liquid crystal elastomer composites with continuous fiber reinforcement

Multifunctional composites have been continuously developed for a myriad of applications with remarkable adaptability to external stimuli and dynamic responsiveness. This study introduces a 4D printing method for liquid crystal elastomer (LCE) composites with continuous fibers and unveils their multifunctional actuation and exciting mechanical responses. During the printing process, the relative motion between the continuous fiber and LCE resin generates shear force to align mesogens and enable the monodomain state of the matrix materials. The printed composite lamina exhibits reversible folding deformations that are programmable by controlling printing parameters. With the incorporation of fiber reinforcement, the LCE composites not only demonstrate high actuation forces but also improved energy absorption and protection capabilities. Diverse shape-changing configurations of 4D composite structures can be achieved by tuning the printing pathway. Moreover, the incorporation of conductive fibers into the LCE matrix enables electrically induced shape morphing in the printed composites. Overall, this cost-effective 4D printing method is poised to serve as an accessible and influential approach when designing diverse applications of LCE composites, particularly in the realms of soft robotics, wearable electronics, artificial muscles, and beyond.

3D printing of reprogrammable liquid crystal elastomers with exchangeable boronic ester bonds

Liquid crystal elastomers (LCEs) are a kind of soft actuating materials with large reversible deformation ability, which can work as the “motor” to exhibit complex deformations and drive the locomotion of soft robots. The deformation of LCEs depends on the three-dimensional (3D) shape of whole structure and alignment patterns of mesogens. Various methods have been employed to fabricate the LCE structure with desired shapes and mesogen alignments. However, conventional 3D printed LCEs require continuous thermal energy input to maintain their actuated shapes. The LCEs cannot be reprocessed and reprogrammed once cured. Herein, we introduce dynamic boronic ester bonds into the ink, with which the printed LCE structures are capable of being reprogrammed from polydomain into monodomain state and vice versa. We further explore the effects of printing parameters and content of dynamic covalent bonds on the actuation performance and reprogramming ability. The actuated shape could be well predicted with finite element method. The dynamic printable LCEs developed here offer new strategy and large design space for LCE structures.

High-field magnetoresistance measurements on Ni75Co25 and Ni40Co60 alloys at 3 K and 300 K

In the present work, a detailed field dependence of the resistivity of Ni75Co25 and Ni40Co60 bulk alloys was measured at T = 3 K and 300 K up to high magnetic fields. The focus of the study was to determine the anisotropic magnetoresistance (AMR) and to get a quantitative description of the field-induced resistivity change, the latter not yet being available for Ni-Co alloys. The AMR parameters were derived from the resistivity data in the magnetically saturated (monodomain) state by using the Kohler analysis. The values of the AMR ratio were found to be close to the relevant previous data both at low and high temperatures. Due to the measurement precision and careful data evaluation, our AMR data obtained on well-characterized samples can be considered as reference values for the bulk state of the investigated compositions. In addition, also the resistivity anisotropy splitting was determined. The experimentally found field dependence of the resistivity at both T = 3 K and 300 K turned out to be at variance with the current theoretical descriptions both for the resistivity increase due to the ordinary magnetoresistance effect being significant at T = 3 K and for the resistivity decrease due to the magnon suppression process at T = 300 K, invoking for a refinement of theory in both cases.

Creation and erasure of polar bubble domains in PbTiO3 films by mechanical stress and light illuminations

The controllable manipulation of polar topological structures (e.g. skyrmion bubble) in ferroelectric materials have been considered as a cornerstone for future programmable nano-electronics. Here, we present the effective creation and erasure of polar bubble states PbTiO3 (PTO) multilayers trigged by mechanical stress and light illumination, respectively. It was found that applying atomic force microscope (AFM) tip force can induced formation of nanoscale bubble domains from the initial monodomain state. Moreover, the created bubble domain can be eliminated by exposure to ultraviolet or infrared light illumination. The above results can be understood by modulation of depolarization screening charges and bias fields, as reflected by scanning Kelvin potential microscopic (SKPM) observations, whereby the flexoelectric effect from the tip force tends to remove the screening charges on top surface and modulate the bias field that favors the formation of bubble state while light illumination tends to recover the screen charges and favor the monodomain state. The results provide a good example for multi-field manipulation of polar topologies, which might create a new avenue towards the immerging new concept electronic devices.

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.

Negative Capacitance in HfO2 Gate Stack Structures With and Without Metal Interlayer

In this work, we experimentally explore and compare FET gate stacks with and without an inner metal plane between a linear dielectric (SiO <sub xmlns:mml="http://www.w3.org/1998/Math/MathML" xmlns:xlink="http://www.w3.org/1999/xlink">2</sub> ) and a ferroelectric layer (Si-doped HfO <sub xmlns:mml="http://www.w3.org/1998/Math/MathML" xmlns:xlink="http://www.w3.org/1999/xlink">2</sub> ) operating in the negative capacitance (NC) regime. The use of nanosecond-range pulses enables us to observe hysteresis-free NC and reconstruct the <inline-formula xmlns:mml="http://www.w3.org/1998/Math/MathML" xmlns:xlink="http://www.w3.org/1999/xlink"> <tex-math notation="LaTeX">${S}$ </tex-math></inline-formula> -shaped polarization-voltage curves. The devices with the inner metal plate show a higher equivalent NC value, which offers the potential for a higher differential amplification in a NC-FET. However, such a NC region is observed over a smaller range of electric field and polarization, which leads to hysteresis. Moreover, the presence of a metal layer in between the ferroelectric and the insulator favors domain formation resulting in destabilization of the NC effect. For the gate structure where the ferroelectric and the insulator are in contact, the <inline-formula xmlns:mml="http://www.w3.org/1998/Math/MathML" xmlns:xlink="http://www.w3.org/1999/xlink"> <tex-math notation="LaTeX">${S}$ </tex-math></inline-formula> -shaped polarization-voltage curve shows a better agreement with Landau–Ginzburg–Devonshire formalism for the monodomain state. The uniform polarization closely mimicking the monodomain state is possible due to the polarization imprint occurring due to the structural asymmetry. By nanometer resolution polarization mapping via off-resonance piezoelectric force microscopy (PFM), we corroborate the presence of imprint, which can intrinsically stabilize one ferroelectric state. Overall, the article provides an experimental demonstration that the absence of the inner metal plane in the gate structures stabilizes the NC regime favorable for hysteresis-free NC-FET.

Simultaneous Large Optical and Piezoelectric Effects Induced by Domain Reconfiguration Related to Ferroelectric Phase Transitions.

Electrical switching of ferroelectric domains and subsequent domain wall motion promotes strong piezoelectric activity, however, light scatters at refractive index discontinuities such as those found at domain wall boundaries. Thus, simultaneously achieving large piezoelectric effect and high optical transmissivity is generally deemed infeasible. Here, it is demonstrated that the ferroelectric domains in perovskite Pb(In1/2 Nb1/2 )O3 -Pb(Mg1/3 Nb2/3 )O3 -PbTiO3 domain-engineered crystals can be manipulated by electrical field and mechanical stress to reversibly and repeatably, with small hysteresis, transform the opaque polydomain structure into a highly transparent monodomain state. This control of optical properties can be achieved at very low electric fields (less than 1.5kV cm-1 ) and is accompanied by a large (>10000 pm V-1 ) piezoelectric coefficient that is superior to linear state-of-the-art materials by a factor of three or more. The coexistence of tunable optical transmissivity and high piezoelectricity paves the way for a new class of photonic devices.

Microstructural evolution in chemical solution deposited PbZrO3 thin films of varying thickness

Compared to the bulky ceramic counterparts, antiferroelectric (AFE) thin films exhibit higher energy-storage performance. It has been demonstrated that the performance of the AFE thin films is strongly affected by the thickness. However, possible changes in the phase structures and microstructures accompanied by varying thicknesses have been less known, which makes it hard to fully understand the physical insight of the thickness effect. Herein, we fabricate a series of PbZrO3 (PZ) thin films by chemical solution deposition whose thickness is approximately proportional to the number of deposition layers, i.e., one to four layers with each layer of about 60 nm in thickness. The detailed structural characterization has been performed by using x-ray diffraction, a scanning electron microscope, and a transmission electron microscope. The films are composed of nanorods oriented normal to the films in which each nanorod maintains single crystalline though segmented by the horizontal interfaces between each of the two neighboring layers, suggesting nearly perfect epitaxy during multilayer growth. The multidomain state is found in three-/four-layer PZ thin films while the one-/two-layer PZ films always present a monodomain state. Meanwhile, incommensurate phases with different modulation periods have been observed in the four-layer PZ films. By comparing the as-observed structural features with the measured electrical properties of different films, it seems that microstructural evolution with the film thickness should not be negligible in evaluating the structure–property relation of PZ-based thin films.

Micromagnetic simulation of domain structure in thin permalloy films with in-plane and perpendicular anisotropy

We investigate the domain structure formation and magnetization processes in thin permalloy films with in-plane and perpendicular magnetic anisotropy by using micromagnetic simulation. We show that the films of thicknesses less than a critical value Lcr are in the monodomain state, and their magnetization processes are specified by the in-plane anisotropy. Above the critical thickness Lcr, the perpendicular anisotropy dominates, leading to the formation of the stripe domain structure that significantly complicates the magnetization reversal. The values of the critical thickness, parameters of the domain structure, and the saturation field obtained from the micromagnetic simulations are compared with the corresponding values calculated using analytical expressions derived by Murayama in the framework of the domain structures theory.

Large electrostrain induced by reversible domain switching in ordered ferroelectric nanostructures with optimized geometric configurations

Large electromechanical response of ferroelectric materials is particularly appealing for applications in functional devices, such as sensors and actuators. For conventional ferroelectric materials, however, the mechanical strain under an external electric field, i.e. the electrostrain, is often limited by the intrinsic electromechanical property of the materials. Domain engineering has been suggested as a practical way to overcome this limitation and to enhance the electrostrain. Here, we show from phase-field simulations that reversible domain switching in ordered ferroelectric nanostructures with optimized geometric configurations can enhance the electrostrain significantly. In the presence of an external electric field, the domains in such nanostructures can switch from a multi-domain state confined by the geometric configurations to a mono-domain state. It is interesting that the domains can switch back to the multi-domain state due to strong internal depolarization fields once the electric field is removed. As a result, accompanying the reversible domain switching behavior, a large and reversible electrostrain can be obtained. Going further, it is found that the temperature dependence of the large electrostrain is similar to that of polarization in such nanostructures. The present work opens a perspective to obtaining large electrostrain in nanoscale ferroelectrics, which holds great promise for designing electromechanical functional devices with high performance.

(Keynote Paper) Mono-Domain Ferrites and Their Implications

Neutron depolarization experiments have shown that the intragranular magnetic domain structure of polycrystalline ferrites exhibits a marked grain size dependence. Below a grain size of around $3~\mu \text{m}$ , the magnetic domain structure changes from the two-domain to the mono-domain state. Ferrites composed of mono-domain grains exhibit low dissipation at megahertz frequencies. This is attributed to the absence of intragranular domain wall movement, i.e., a microscopic origin for dissipation in ferrites has been identified. The implications of this clear observation and evidence for a transition from the mono- to two-domain state in ferrites for micromagnetic theory when a single particle becomes monodomain, as well as for the initial permeability mechanisms in polycrystalline ferrites, are discussed.

Sample-size dependent temperature dependence of the spontaneous magnetization

It is shown that the precise temperature dependence of the spontaneous magnetization depends on the domain structure and, additionally, on the macroscopic dimensions of the sample. In the multi-domain zero-field ground state of cubic ferromagnets (or antiferromagnets) with half-integer spin, thermal decrease of the spontaneous magnetization is by universal T2 function up to crossover to critical power function. Power functions of temperature that hold over a large temperature range and are independent of spin structure are the typical indication that the spin dynamics is controlled by a boson field. For the magnets with half-integer spin, the T2 function means a three-dimensional boson field. In the mono-domain state prepared by ferromagnetic saturation, all moments are oriented parallel to the field axis. For this one-dimensional spin configuration the boson field can be anticipated to be one-dimensional and the spontaneous magnetization should decrease according to universal T5/2 function (for S = half-integer). However, only for sufficiently large samples the T5/2 function is confirmed. For smaller samples successive crossover events in the sequence T2 → T3/2 → T5/2 can occur for increasing temperature. Occurrence of boson fields with a higher dimensionality (T2, T3/2) in the state of ferromagnetic saturation can be explained by scattering processes of the bosons at the inner surface of the sample. When the diameter of the sample is less than the mean free path of the bosons, all bosons will be reflected (or scattered) at the inner surface of the sample and the resulting boson field can become three-dimensional (T2 universality class). A one-dimensional spin orientation due to the applied demagnetization field but a three-dimensional boson field that controls spin dynamics is possible only for the T2 universality class because there is nearly no interaction between boson field and spins (magnons) in this universality class. With increasing temperature the mean free path of the bosons decreases and only a fraction of the bosons gets scattered at the inner surface of the sample. Crossover to T3/2 function and, eventually, to T5/2 function then can occur. A similar situation as for the polarized ferromagnets is observed in the axial-symmetric zero-field ground state of the hcp ferromagnet cobalt. Only for sufficiently large samples scattering of the bosons at the inner surface of the sample is of no importance and the intrinsic T5/2 function, typical for parallel alignment of all spins, shows up. The mean free path of the bosons can be estimated to be of the order of a few mm for T → 0.

Accounting for the various contributions to pyroelectricity in lead zirconate titanate thin films

An understanding of the pyroelectric coefficient and particularly its relationship with the applied electric field is critical to predicting the device performance for infrared imaging, energy harvesting, and solid-state cooling devices. In this work, we compare direct measurements of the pyroelectric effect under pulsed heating to the indirect extraction of the pyroelectric coefficient from adiabatic hysteresis loops and predictions from Landau-Devonshire theory for PbZr0.52Ti0.48O3 (PZT 52/48) on platinized silicon substrates. The differences between these measurements are explained through a series of careful measurements that quantify the magnitude and direction of the secondary and field-induced pyroelectric effects. The indirect measurement is shown to be up to 25% of the direct measurement at high fields, while the direct measurements and theoretical predictions converge at high fields as the film approaches a mono-domain state. These measurements highlight the importance of directly measuring the pyroelectric response in thin films, where non-intrinsic effects can be a significant proportion of the total observed pyroelectricity. Material and operating conditions are also discussed which could simultaneously maximize all contributions to pyroelectricity.

In Ukrainian

The investigation results are shown directed onto development of the concept of creation of magnetosensitive nanocomposites (NC) with multilevel hierarchical nanoarchitecture and functions of biomedical nanorobots. We synthesized nanosized magnetite in monodomain state and magnetosensitive NC based on that (Fe3O4/dimercaptosuccinic acid (DMSA), Fe3O4/γ-aminopropylsiloxane (γ-APS), Fe3O4/polyacrylamide (PAA), Fe3O4/hydroxyapatite (HA), Fe3O4/SiO2, Fe3O4/TiO2, Fe3O4/Al2О3). Isotherms and adsorption kinetics of cisplatin were studied depending on chemical nature of the surface of nanostructures. Adsorption of doxorubicin (DOX) onto the surface of Fe3O4/HА NC from solution in physiological liquid was studied. Magnetic fluids containing Fe3O4/HА/DOX NC were produced and investigated. Using an ensemble of Fe3O4 carriers as a superparamagnetic probe, Langeven’s paramagnetism theory, we appreciated size parameters of their shell, which was confirmed by independent measurements of specific surface area of the nanostructures and thermodynamic sedimentation stability of the corresponding magnetic fluids. The results obtained may be used in development of new forms of magnetocarried medical remedies for targeted delivery, and adsorbents based on NC of superparamagnetic core-shell type with multilevel nanoarchitecture, and for determination, control and optimization of size parameters of its components.

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.

Anisotropy of infrared-active phonon modes in the monodomain state of tetragonal SrTiO3 (110)

With infrared and terahertz ellipsometry we investigated the anisotropy of the infrared active phonon modes in SrTiO3 (110) single crystals in the tetragonal state below the so-called antiferrodistortive transition at T* = 105 K. In particular, we show that the anisotropy of the oscillator strength of the so-called R-mode, which becomes weakly infrared active below T*, is a valuable indicator for the orientation of the structural domains. Our results reveal that a mono-domain state with the tetragonal axis (c-axis) parallel to the [001] direction can be created by applying a moderate uniaxial stress of about 2.3 MPa along the [1-10] direction (with a mechanical clamp). The resulting, intrinsic splitting of the infrared-active phonon modes is reported.

Structural phase transition in a perovskite-type NH3(CH2)3NH3CuCl4 crystal – X-ray and optical studies

ABSTRACTX-ray powder studies and optical studies (polarized microscopic observation and linear birefringence studies) of the crystal NH3(CH2)3NH3CuCl4 are presented. The X-ray powder studies revealed a change of symmetry from orthorhombic room-temperature phase to monoclinic phase above 434 K. A reversible phase transition of the first order at 434 K on heating and 432 K on cooling was observed in birefringence studies. Optical polarized microscopic observation revealed monodomain and multidomain states in the room-temperature orthorhombic phase with domain walls in (110) and (1-10) planes. The hypothetical prototypic phase is expected to be tetragonal. The change of symmetry from orthorhombic to monoclinic and expected domain structure was found above 434 K in the (010) plane.

Magnetic structure and effect of magnetic field on its domain structure in magnetoelectric Ba1.3Sr0.7CoZnFe11AlO22

The magnetic structure and the effect of a magnetic field on its domain structure were investigated in a magnetoelectric Y-type hexaferrite, Ba1.3Sr0.7CoZnFe11AlO22, by means of mapping with a micro-focused and circularly polarized X-ray beam in the resonant X-ray diffraction. It was revealed that this hexaferrite exhibits a magnetic order characterized by two distinct antiferromagnetic components: incommensurate helical and commensurate collinear ones, which can be explained as the development of the so-called alternating longitudinal conical structure. A multi-domain state due to the handedness of the helical component, i.e., spin-chirality, is transformed into nearly a mono-domain one by using only a magnetic field. Furthermore, the sign of the spin-chirality in the mono-domain state is reversed by reversing the sign of a magnetic field. These results demonstrate that the spin-chirality in this hexaferrite can be manipulated by a magnetic field alone at room temperature.

Tuning the caloric response of BaTiO3 by tensile epitaxial strain

We investigate the effect of epitaxial strain on the electrocaloric effect (ECE) in BaTiO3 by means of ab-initio–based molecular-dynamics simulations. We show that tensile strain can be used to optimize the operation range for ferroic cooling. Strain in the range of ≤ 1% can be used to shift the operation temperature by several hundreds of kelvin both to higher and lower temperatures, depending on the direction of the external field. In addition, the transformation between multi-domain and mono-domain states, induced by an in-plane electric field, results in an additional peak of the adiabatic temperature change at lower temperatures, and a broad temperature interval where the caloric response scales linearly with the applied field strength, even up to very high fields.