Ferroelectric Polarization Switching Research Articles

Quantitative Characterization of Ferroelectric/Dielectric Interface Traps by Pulse Measurements

The ferroelectric (FE) polarization switching behavior in the HfZrO <sub xmlns:mml="http://www.w3.org/1998/Math/MathML" xmlns:xlink="http://www.w3.org/1999/xlink">2</sub> (HZO) FE/dielectric (FE/DE) stack is investigated systematically by charge responses from pulse measurements. The trapped charge density at the FE/DE interface related with the FE polarization switching is found to be 1.2 × 10 <sup xmlns:mml="http://www.w3.org/1998/Math/MathML" xmlns:xlink="http://www.w3.org/1999/xlink">14</sup> cm <sup xmlns:mml="http://www.w3.org/1998/Math/MathML" xmlns:xlink="http://www.w3.org/1999/xlink">-2</sup> according to the leakage-current-assist polarization switching mechanism. Furthermore, by the time-dependent nonswitching charge responses, the extra FE/DE interface trap density of 1.1 × 10 <sup xmlns:mml="http://www.w3.org/1998/Math/MathML" xmlns:xlink="http://www.w3.org/1999/xlink">13</sup> cm <sup xmlns:mml="http://www.w3.org/1998/Math/MathML" xmlns:xlink="http://www.w3.org/1999/xlink">-2</sup> is confirmed, which is not related but can be detected along with the FE polarization switching. The quantitative characterization reveals the huge amount of FE/DE interface traps and their dominant role in the FE operation of HZO FE/DE stack, which improves the proposed leakagecurrent-assist polarization switching model. This improved model provides a more comprehensive understanding of the polarization switching in the HZO FE/DE stack and new insights on HZO negative-capacitance (NC) and FE fieldeffect transistors (FETs).

МАТЕМАТИЧЕСКИЕ МОДЕЛИ ПОЛЯРИЗАЦИОННЫХ ХАРАКТЕРИСТИК СЕГНЕТОЭЛЕКТРИКОВ В РАМКАХ ТЕОРИИ ЛАНДАУ - ГИНЗБУРГА - ДЕВОНШИРА

The paper presents the overview and implementation of mathematical models of ferroelectric polarization characteristics within the framework of the Landau - Ginzburg theory. Mathematical models of polarization switching in ferroelectrics are formalized by means of several types of differential problems. Based on difference methods the computational schemes are constructed for various modifications of the Landau - Khalatnikov model. Numerical simulation of the polarization hysteresis in ferroelectrics with the first-order phase transition is performed. The computational results obtained in Matlab are compared with the experimental data.

A Smarter Pavlovian Dog with Optically Modulated Associative Learning in an Organic Ferroelectric Neuromem.

Associative learning is a critical learning principle uniting discrete ideas and percepts to improve individuals' adaptability. However, enabling high tunability of the association processes as in biological counterparts and thus integration of multiple signals from the environment, ideally in a single device, is challenging. Here, we fabricate an organic ferroelectric neuromem capable of monadically implementing optically modulated associative learning. This approach couples the photogating effect at the interface with ferroelectric polarization switching, enabling highly tunable optical modulation of charge carriers. Our device acts as a smarter Pavlovian dog exhibiting adjustable associative learning with the training cycles tuned from thirteen to two. In particular, we obtain a large output difference (>103), which is very similar to the all-or-nothing biological sensory/motor neuron spiking with decrementless conduction. As proof-of-concept demonstrations, photoferroelectric coupling-based applications in cryptography and logic gates are achieved in a single device, indicating compatibility with biological and digital data processing.

Ferroelectric state and polarization switching behaviour of ultrafine BaTiO3 nanoparticles with large-scale size uniformity

A coherently non-centrosymmetric structure and remarkable macroscopic ferroelectric response of 4.5 nm BTO nanocrystals are reported.

Magnetoelectric Coupling and Decoupling in Multiferroic Hexagonal YbFeO3 Thin Films

The coupling between ferroelectric and magnetic orders in multiferroic materials and the nature of magnetoelectric (ME) effects are enduring experimental challenges. In this work, we have studied the response of magnetization to ferroelectric switching in thin-film hexagonal YbFeO3, a prototypical improper multiferroic. The bulk ME decoupling and potential domain-wall ME coupling were revealed using x-ray magnetic circular dichroism (XMCD) measurements with in-situ ferroelectric polarization switching. Our Landau theory analysis suggests that the bulk ME-coupled ferroelectric switching path has a higher energy barrier than that of the ME-decoupled path; this extra barrier energy is also too high to be reduced by the magneto-static energy in the process of breaking single magnetic domains into multi-domains. In addition, the reduction of magnetization around the ferroelectric domain walls predicted by the Landau theory may induce the domain-wall ME coupling in which the magnetization is correlated with the density of ferroelectric domain walls. These results provide important experimental evidence and theoretical insights into the rich possibilities of ME couplings in hexagonal ferrites, such as manipulating the magnetic states by an electric field.

Large Piezoelectric Response and Ferroelectricity in Li and V/Nb/Ta Co-Doped w-AlN.

Enhancement of piezoelectricity in w-AlN is desired for many devices including resonators for next-generation wireless communication systems, sensors, and vibrational energy harvesters. Based on density functional theory, we show that Li and X (X = V, Nb, and Ta) co-doping in 1Li:1X ratio transforms brittle w-AlN crystal to ductile, along with broadening the compositional freedom for significantly enhanced piezoelectric response, promising them to be good alternatives to expensive Sc. Interestingly, these co-doped w-AlN also show quite large spontaneous electric polarization (e.g., about 1 C/m2 for Li0.125X0.125Al0.75N) with the possibility of ferroelectric polarization switching, opening new possibilities in wurtzite nitrides. An increase in piezoelectric stress constant (e33) with a decrease in elastic constant (C33) results in an enhancement of piezoelectric strain constant (d33), which is desired for improving the performance of bulk acoustic wave (BAW) resonators for high-frequency radio frequency (RF) signals. Also, these co-doped w-AlN are potential lead-free piezoelectric materials for energy harvesting and sensors as they improve the longitudinal electromechanical coupling constant (K332), transverse piezoelectric strain constant (d31), and figure of merit (FOM) for power generation. However, the enhancement in K332 is not as pronounced as that in d33 because co-doping increases dielectric constant. The longitudinal acoustic wave velocity (7.09 km/s) of Li0.1875Ta0.1875Al0.625N is quite comparable to that of commercially used piezoelectric LiNbO3 or LiTaO3 in special cuts (about 5-7 km/s) despite the fact that the acoustic wave velocities, important parameters for designing resonators or sensors, decrease with co-doping or Sc concentration.

TiN/Gd:HfO2/TiN capacitors grown by PEALD showing high endurance ferroelectric switching

TiN/Gd:HfO2/TiN metal/ferroelectric/metal structures were elaborated in one batch by plasma enhanced atomic layer deposition. The crystal structure and ferroelectric properties of 12-nm-thick Gd-doped HfO2 thin films are investigated. The modulation of the Gd content within the HfO2 layer leads to a subsequent variation of crystalline phases; predominance of the orthorhombic phase correlates with a maximum 2·Pr value of 30 μC/cm2 for 1.8% of Gd doping as well as a ferroelectric polarization switching endurance up to 7 × 109 cycles. These remarkable properties of Gd:HfO2 material compared to previous works are likely the consequence of nonexposure to air of metal/insulator interfaces during stack deposition, preventing their oxidation and/or carbon contamination.

Large Polarization Switching and High-Temperature Magnetoelectric Coupling in Multiferroic GaFeO3 Systems.

GaFeO3-type iron oxides are promising multiferroics due to the coexistence of large spontaneous magnetization and polarization near room temperature. However, the high leakage current and difficulties associated with synthesizing single crystals make it difficult to achieve two important features in the system: a large ferroelectric polarization switching and magnetoelectric coupling at a high-temperature region. Herein, we report successful achievement of these features by preparing high-quality Sc-doped GaFeO3 single crystals (ScxGa1-x/2Fe1-x/2O3 with x = 0-0.3) using the floating zone method. The x ≥ 0.05 crystals exhibit a leakage current 104 times lower than the x = 0 crystals, highlighting the importance of Sc doping. Because of the reduced leakage current, the Sc-doped crystals exhibit large ferroelectric polarization switching along the c-axis with a remanent polarization of 22-25 μC/cm2, which is close to the theoretically predicted polarization value of 25-28 μC/cm2. In addition, the Sc-doped crystals exhibit ferrimagnetism with magnetic anisotropy along the a-axis. Furthermore, a magnetic-field-induced modulation of polarization is observed in the x = 0.15 crystal even at a relatively high temperature, i.e., 100 K.

Ferroelastic Nanodomain-mediated Mechanical Switching of Ferroelectricity in Thick Epitaxial Films.

Mechanical switching of ferroelectric polarization, typically realized via a scanning probe, holds promise in (multi)ferroic device applications. Whereas strain gradient-associated flexoelectricity has been regarded to be accountable for mechanical switching in ultrathin (<10 nm) films, such mechanism can hardly be extended to thicker materials due to intrinsic short operating lengths of flexoelectricity. Here, we demonstrate robust mechanical switching in ∼100 nm thick Pb(Zr0.2Ti0.8)O3 epitaxial films with a characteristic microstructure consisting of nanosized ferroelastic domains. Through a combination of multiscale structural characterizations, piezoresponse force microscopy, and phase-field simulations, we reveal that the ferroelastic nanodomains effectively mediate the 180° switching nucleation in a dynamical manner during tip scanning. Coupled with microstructure engineering, this newly revealed mechanism could boost the utility of mechanical switching through extended material systems. Our results also provide insight into competing polarization switching pathways in complex ferroelectric materials, essential for understanding their electromechanical response.

Interplay between morphology and magnetoelectric coupling in Fe/PMN-PT multiferroic heterostructures studied by microscopy techniques

A ferromagnetic (FM) thin film deposited on a substrate of $\mathrm{Pb}({\mathrm{Mg}}_{1/3}{\mathrm{Nb}}_{2/3}){\mathrm{O}}_{3}\text{\ensuremath{-}}{\mathrm{PbTiO}}_{3}$ (PMN-PT) is an appealing heterostructure for the electrical control of magnetism, which would enable nonvolatile memories with ultralow-power consumption. Reversible and electrically controlled morphological changes at the surface of PMN-PT suggest that the magnetoelectric effects are more complex than the commonly used ``strain-mediated'' description. Here we show that changes in substrate morphology intervene in magnetoelectric coupling as a key parameter interplaying with strain. Magnetic-sensitive microscopy techniques are used to study magnetoelectric coupling in Fe/PMN-PT at different length scales, and compare different substrate cuts. The observed rotation of the magnetic anisotropy is connected to the changes in morphology, and mapped in the crack pattern at the mesoscopic scale. Ferroelectric polarization switching induces a magnetic field-free rotation of the magnetic domains at micrometer scale, with a wide distribution of rotation angles. Our results show that the relationship between the rotation of the magnetic easy axis and the rotation of the in-plane component of the electric polarization is not straightforward, as well as the relationship between ferroelectric domains and crack pattern. The understanding and control of this phenomenon is crucial to develop functional devices based on FM/PMN-PT heterostructures.

Controlling bimerons as skyrmion analogues by ferroelectric polarization in 2D van der Waals multiferroic heterostructures

Atom-thick van der Waals heterostructures with nontrivial physical properties tunable via the magnetoelectric coupling effect are highly desirable for the future advance of multiferroic devices. In this work on LaCl/In2Se3 heterostructure consisting of a 2D ferromagnetic layer and a 2D ferroelectric layer, reversible switch of the easy axis and the Curie temperature of the magnetic LaCl layer has been enabled by switching of ferroelectric polarization in In2Se3. More importantly, magnetic skyrmions in the bimerons form have been discovered in the LaCl/In2Se3 heterostructure and can be driven by an electric current. The creation and annihilation of bimerons in LaCl magnetic nanodisks were achieved by polarization switching. It thus proves to be a feasible approach to achieve purely electric control of skyrmions in 2D van der Waals heterostructures. Such nonvolatile and tunable magnetic skyrmions are promising candidates for information carriers in future data storage and logic devices operated under small electrical currents.

Band Alignment of ScxAl1–xN/GaN Heterojunctions

ScAlN is an emergent ultrawide-band-gap material with both a high piezoresponse and demonstrated ferroelectric polarization switching. Recent demonstration of epitaxial growth of ScAlN on GaN has unlocked prospects for new high-power transistors and nonvolatile memory technologies fabricated from these materials. An understanding of the band alignments between ScAlN and GaN is crucial in order to control the electronic and optical properties of engineered devices. To date, there have been no experimental studies of the band offsets between ScAlN and GaN. This work presents optical characterization of the band gap of molecular beam epitaxy grown ScxAl1-xN using spectroscopic ellipsometry and measurements of the band offsets of ScxAl1-xN with GaN using X-ray photoemission spectroscopy, along with a comparison to first-principles calculations. The band gap is shown to continuously decrease as a function of increasing ScN alloy fraction with a negative bowing parameter. Furthermore, a crossover from straddling (type-I) to staggered (type-II) band offsets is demonstrated as Sc composition increases beyond approximately x = 0.11. These results show that the ScAlN/GaN valence band alignment can be tuned by changing the Sc alloy fraction, which can help guide the design of heterostructures in future ScAlN/GaN-based devices.

Huge Piezoelectric Response of LaN-based Superlattices.

We construct LaN-based artificial superlattices to investigate the ferroelectricity and piezoelectricity using the volume matching conditions of the parent components that soften the elastic constant C33 and increase the piezoelectric modulus d33. The proposed superlattice consists of LaN and YN (or LaN and ScN) buckled monolayers alternately arranged along the crystallographic c-direction. The structure of polar wurtzite (w-LaYN/w-LaScN) is both mechanically and dynamically stable, and the computed energy barrier makes the ferroelectric polarization switching possible. We show that the epitaxial strain can modify the spontaneous ferroelectric polarization as well as d33. The LaN/YN superlattice exhibits a huge piezoelectric response in the unstrained state, due to their small c/a value and extremely soft C33. In addition, the epitaxial strain is revealed as effective control of the nature (indirect and direct) and value of the electronic band gap.

Key Role of Oxygen-Vacancy Electromigration in the Memristive Response of Ferroelectric Devices

Ferroelectric memristors are intensively studied due to their potential implementation in data storage and processing devices. In this work we show that the memristive behavior of metal/ferroelectric oxide/metal devices relies on the competition of two effects: the modulation of metal/ferroelectric interface barriers by the switchable ferroelectric polarization and the electromigration of oxygen vacancies, with the depolarizing field playing a fundamental role in the latter. We simulate our experimental results with a phenomenological model that includes both effects and we reproduce several non-trivial features of the electrical response, including resistance relaxations observed after external poling. Besides providing insight into the underlying physics of these complex devices, our work suggests that it is possible to combine non-volatile and volatile resistive changes in single ferroelectric memristors, an issue that could be useful for the development of neuromorphic devices.

Electrically driven transient and permanent phase transformations in highly strained epitaxial BiFeO3 thin films

Electric-field-driven phase transformation phenomena in multiferroic BiFeO3 are directly linked to the functionalities of electronic devices based on multiferroic materials. Understanding how the transformation evolves at the nanoscale under the influence of an electric field will provide fascinating insights into key parameters that utilize the transformation features. Here, we report both the electric-field-driven transient and permanent phase transformations in highly strained BiFeO3 thin films and their transformation dynamics at the nanoscale. We found that two distinct transient and permanent phase transformations were triggered below and above a coercive voltage of the polymorphic phase, indicating that ferroelectric polarization switching could promote permanent phase transformations. We also found that the transient transformations evolve via complex phase boundary motions between the coexisting phases, whereas permanent transformations occurred via nucleation of the other phases.

Current-voltage characteristics of phase boundaries PVDF-TrFE(70/30)/PANI nanocomposite

In this work, the local current-voltage characteristics of nanocomposite phase boundaries in the form of a poly(vinylidene fluoride-trifluoroethylene) (PVDF-TrFE) (70/30) matrix filled with conductive polyaniline (PANI) particles are studied by conductive atomic force microscopy. At negative external bias voltages, these dependencies are shown to have an interval with a negative differential resistance. This fact is caused by the switching of ferroelectric polarization of individual nanocrystallites PVDF-TrFE located near the phase boundaries in the amorphous matrix volume. The obtained results confirm assumptions about the memristive properties of the investigated nanocomposites.

Hydrothermal growth of c-axis oriented ferroelectric (Bi1/2K1/2)TiO3 films on metal substrates

Ferroelectric films fabricated on metal substrates are desirable for use in piezoelectric vibration energy harvesters. In this report, we demonstrate that dense films of lead-free ferroelectric (Bi1/2K1/2)TiO3 (BKT) with preferred c-axis orientation can be grown on nickel-based alloy substrates by utilizing the hydrothermal synthesis method. A buffer layer of LaNiO3 (LN) was formed on the substrates by the sol-gel spin coating method, and then BKT was grown by a hydrothermal reaction at a low temperature of 150 °C. The surface structure and thickness of the final BKT films were found to strongly depend on the numbers of the deposition cycles for LN and BKT, respectively. As a result, highly c-axis oriented BKT films with a smooth surface and a thickness up to 830 nm were obtained. Although the as-deposited BKT films were suggested to contain hydroxyl groups in their crystal lattice, a post-annealing process at 650 °C in air was found to be effective to remove them. The polarization response of the annealed BKT film proved the ferroelectric polarization switching in the film.

Polarization Switching in 2D Nanoscale Ferroelectrics: Computer Simulation and Experimental Data Analysis.

The polarization switching kinetics of nanosized ferroelectric crystals and the transition between homogeneous and domain switching in nanoscale ferroelectric films are considered. Homogeneous switching according to the Ginzburg-Landau-Devonshire (LGD) theory is possible only in two-dimensional (2D) ferroelectrics. The main condition for the applicability of the LGD theory in such systems is its homogeneity along the polarization switching direction. A review is given of the experimental results for two-dimensional (2D) films of a ferroelectric polymer, nanosized barium titanate nanofilms, and hafnium oxide-based films. For ultrathin 2D ferroelectric polymer films, the results are confirmed by first-principle calculations. Fitting of the transition region from homogeneous to domain switching by sigmoidal Boltzmann functions was carried out. Boltzmann function fitting data enabled us to correctly estimate the region sizes of the homogeneous switching in which the LGD theory is valid. These sizes contain several lattice constants or monolayers of a nanosized ferroelectrics.

Theoretical and numerical analysis of the Landau–Khalatnikov model of ferroelectric hysteresis

An initial-boundary value problem for the reaction-diffusion Landau–Khalatnikov equation applied to describe polarization switching in ferroelectrics is studied from both theoretical and computational points of view. The existence and uniqueness of a weak solution of the initial-boundary value problem are proved. An absolutely stable monotonic numerical scheme of the second-order accuracy combined with an iterative procedure is constructed. Numerical simulation of the polarization hysteresis in ferroelectrics with the first-order phase transition is performed. The results of the computations obtained on the base of different modifications of the model are compared with experimental data. An important role of the diffusion term and its scaling effect for an adequate description of the polarization switching in ferroelectrics are shown.

Toward Intrinsic Ferroelectric Switching in Multiferroic BiFeO_{3}.

Using pulsed ferroelectric measurements, we probe switching dynamics in multiferroic BiFeO_{3}, revealing low-ns switching times and a clear pathway to sub-ns switching. Our data is well described by a nucleation and growth model, which accounts for the various timescales in the switching process, namely (1)the ferroelectric polarization switching (bound-charge) dynamics and (2)the RC-limited movement of free charge in the circuit. Our model shows good agreement with observed data and begins to bridge the gap between experiment and theory, indicating pathways to study ferroelectric switching on intrinsic timescales.