Ferroelectric Thin Films Research Articles

Robust Tunability and Newly Emerged Q Resonance of Ba0.8Sr0.2TiO3-Based Microwave Capacitors under Gamma Irradiations.

The complex resonance of dielectric quality factor Q, combined with a capacitance tunability n higher than 3:1 without any dispersion, was achieved in the voltage-tunable interdigital capacitors (IDCs) based on epitaxial Ba0.8Sr0.2TiO3 ferroelectric thin films across the microwave L (1-2 GHz), S (2-4 GHz), and C (4-8 GHz) bands at room temperature. The resonant Q and n features were driven by the microwave responses of the ferroelectric nanodomains engineered in the films. To promote their application in space radiation environments, the evolutions of Q and n both as functions of frequency f (1-8 GHz) and applied electric field E (0-240 kV/cm) were systematically investigated under a series of gamma-ray irradiations up to 100 kGy. The robust capacitance tunability was accompanied by the emergence of an additional Q resonance at 2.3 GHz in most post-irradiated devices, which is ascribed to extra polar nanoregions of expanded surface lattices associated with oxygen vacancies induced by irradiations.

Ultralow Strain-Induced Emergent Polarization Structures in a Flexible Freestanding BaTiO3 Membrane.

The engineering of ferroic orders, which involves the evolution of atomic structure and local ferroic configuration in the development of next-generation electronic devices. Until now, diverse polarization structures and topological domains are obtained in ferroelectric thin films or heterostructures, and the polarization switching and subsequent domain nucleation are found to be more conducive to building energy-efficient and multifunctional polarization structures. In this work, a continuous and periodic strain in a flexible freestanding BaTiO3 membrane to achieve a zigzag morphology is introduced. The polar head/tail boundaries and vortex/anti-vortex domains are constructed by a compressive strain as low as ≈0.5%, which is extremely lower than that used in epitaxial rigid ferroelectrics. Overall, this study c efficient polarization structures, which is of both theoretical value and practical significance for the development of next-generation flexible multifunctional devices.

Advancing Energy‐Storage Performance in Freestanding Ferroelectric Thin Films: Insights from Phase‐Field Simulations

AbstractAdvances in flexible electronics are driving the development of ferroelectric thin‐film capacitors toward flexibility and high energy storage performance. In the present work, the synergistic combination of mechanical bending and defect dipole engineering is demonstrated to significantly enhance the energy storage performance of freestanding ferroelectric thin films, achieved through the generation of a narrower and right‐shifted polarization‐electric field hysteresis loop. The recoverable energy storage density of freestanding PbZr0.52Ti0.48O3 thin films increases from 99.7 J cm−3 in the strain (defect) ‐free state to 349.6 J cm−3, marking a significant increase of 251%. The collective impact of the flexoelectric field, bending tensile strain, and defect dipoles contributes to this enhancement. The demonstrated synergistic optimization strategy has potential applicability to flexible ferroelectric thin film systems. Moreover, the energy storage properties of flexible ferroelectric thin films can be further fine‐tuned by adjusting bending angles and defect dipole concentrations, offering a versatile platform for control and performance optimization.

Energy storage properties influenced by relaxor ferroelectric properties dependent on the growth direction of epitaxial Bi2SiO5 thin films

Ferroelectric Bi2SiO5 (BSO) thin films were deposited by pulsed laser deposition on Nb-doped (100), (110) and (111) SrTiO3 (Nb:STO) substrates, resulting in (001)-, (113)- and (204)-oriented epitaxial films. Due to the crystallinity of BSO, in which the Bi2O2 layers are formed perpendicular to the c-axis direction, the (001)-oriented epitaxial BSO thin film showed the lowest remanent polarization and the best leakage current characteristics. On the other hand, the (113)- and (204)-oriented films showed an increase in remanent polarization due to the improvement of a-oriented crystallinity. Through experiments using vertical and lateral piezoresponse force microscopy, it has been confirmed that the distribution of in-plane-oriented domains reducing remanent polarization decreases in the order of (001)-, (113)- and (204)-oriented epitaxial BSO thin films. The epitaxial BSO thin films that exhibit ferroelectric hysteresis loops similar to the relaxor ferroelectric thin films tended to have improved energy storage characteristics as a result of improved remanent polarization and saturation polarization. In particular, the (113)-oriented epitaxial BSO thin film showed a high recoverable energy density of about 41.6 J cm−3 and an energy storage efficiency of about 85.6%.

Polarization fatigue mechanism of laminated hafnium zirconium oxide ferroelectric thin films

Laminated HfO2-based ferroelectric thin films (FE-HfO2) have offered unexpected opportunities to implement the high-density ferroelectric memory and on chip piezoelectric or pyroelectric devices. But the polarization fatigue performance is poor and the underlying mechanism is unknown. In this work, we comprehensively investigate the polarization fatigue behaviors of Hf0.5Zr0.5O2(HZO)/Al2O3/HZO laminated thin films. Several possible mechanisms for the fatigue performances are discussed in detail. On basis of the analysis of micro-structures and domain switching dynamics before and after fatigue, we confirm that domain wall pinning phenomenon exists in the fatigued laminated HZO, without field-induced phase transition as well as thickness and chemical properties changes of interfacial layers. Moreover, we discover by a pulse measurement method that domain wall pinning induced by the increase of Al2O3/HZO interface trap charge is responsible for the fatigue performances of the laminated films. This work will provide useful guidance for designing high-reliability laminated FE-HfO2, and contribute to understand the physical mechanisms of FE-HfO2.

Artificial synaptic properties of zirconium-doped barium titanate film for neuromorphic computing

The traditional Von Neumann Architecture relies on the separation of memory and CPU, leading to bottlenecks like slow data transfer and high energy consumption. This is especially challenging when addressing the demands of large-scale parallel computing tasks such as artificial intelligence. Devices capable of simulating synaptic properties have gotten significant attention. Neuromorphic computing combines those devices with methods that work with neural networks. They are considered a viable approach to overcoming the Von Neumann Architecture bottleneck. This paper presents a Zr-doped BaTiO3 ferroelectric thin film prepared by a sol-gel process, which mimics the synaptic properties of the nerve: Short-Term Synaptic Plasticity (STP), paired-pulse facilitated (PPD), Long-Term Synaptic Plasticity (LTP) and Spike-Timing-Dependent Plasticity (STDP). An enhanced stochastic adaptive method is used to a built-in Convolutional Neural Network (CNN) to evaluate the device's neuromorphic computing capabilities. According to the results, the device obtains recognition accuracies of 96.5 % and 75.1 % for the MNIST and Fashion-MNIST datasets, respectively. This significantly contributes to the advancement of ferroelectric materials in neuromorphic computing applications.

Ferroelastically protected reversible orthorhombic to monoclinic-like phase transition in ZrO2 nanocrystals.

Robust ferroelectricity in nanoscale fluorite oxide-based thin films enables promising applications in silicon-compatible non-volatile memories and logic devices. However, the polar orthorhombic (O) phase of fluorite oxides is a metastable phase that is prone to transforming into the ground-state non-polar monoclinic (M) phase, leading to macroscopic ferroelectric degradation. Here we investigate the reversibility of the O-M phase transition in ZrO2 nanocrystals via in situ visualization of the martensitic transformation at the atomic scale. We reveal that the reversible shear deformation pathway from the O phase to the monoclinic-like (M') state, a compressive-strained M phase, is protected by 90° ferroelectric-ferroelastic switching. Nevertheless, as the M' state gradually accumulates localized strain, a critical tensile strain can pin the ferroelastic domain, resulting in an irreversible M'-M strain relaxation and the loss of ferroelectricity. These findings demonstrate the key role of ferroelastic switching in the reversibility of phase transition and also provide a tensile-strain threshold for stabilizing the metastable ferroelectric phase in fluorite oxide thin films.

High-Performance Ferroelectric Thin Film Transistors with Large Memory Window Using Epitaxial Yttrium-Doped Hafnium Zirconium Gate Oxide.

Preventing ferroelectric materials from losing their ferroelectricity over a low thickness of several nanometers is crucial in developing multifunctional nanoelectronics. Epitaxially grown 5 at. % yttrium-doped Hf0.5Zr0.5O2 (YHZO) thin films exhibit an atomically smooth surface, an ability to maintain ferroelectricity even at a thickness of 10 nm, and excellent insulating properties, making them suitable for use as gate oxides in ferroelectric thin film transistors (FeTFTs). Through the epitaxial growth of a YHZO/La0.67Sr0.33MnO3 (LSMO)/SrTiO3 (STO) heterostructure, YHZO effectively retains its ferroelectricity and orthorhombic single phase, leading to enhancing electron mobility (∼19.74 cm2 V-1 s-1) and memory window (3.7 V) in the amorphous InGaZnO4 (a-IGZO)/YHZO/LSMO/STO FeTFTs. These FeTFTs demonstrate a consistent memory function with remarkable endurance (∼106 cycles) and retention (∼104 s). Furthermore, they sustain a constant memory window even under ±6 V bias stress for 104 s and exhibit excellent stability even under ±6 V/1 ms pulse cycling for 107 cycles. For comparison, a transistor with the same structure was fabricated using epitaxial nonferroelectric LaAlO3 (LAO) and epitaxial undoped Hf0.5Zr0.5O2 (HZO) as alternatives to YHZO. This study presents a novel approach to exploit the potential of YHZO in FeTFTs, contributing to the development of next-generation logic-in-memory.

Multilevel Ferroelectric Domain Wall Memory for Neuromorphic Computing

AbstractLow‐power and parallel processing Neuromorphic computing that imitates on the human brain's extraordinary data processing and learning capabilities is promising in non‐von Neumann application platforms in the post‐Moore era. Ferroelectric domain walls appearing as nanoscale topological defects in solids exhibit coexisting ordering parameters besides the spontaneous polarization, leading to the emergence of rich physics and electronic effects in the development of neuromorphic electronics that go beyond the conventional CMOS. In this study, the four‐state domain wall memory is developed on LiNbO3 ferroelectric thin films integrated with Si substrates, where each state can be stably manipulated at a specific low voltage, showcasing outstanding fatigue resistance and retention performance. The constructed crossbar array that functions as a kernel for image convolution can be used to implement processing operations like image filtering, sharpness enhancement, and edge detection. Additional simulation from a convolutional neural network model shows 96.98% accuracy on the Modified National Institute of Standards and Technology handwritten digits dataset. The stable multi‐state domain wall memory provides a new approach for computing and promotes research in domain wall electronics to meet future enormous demands of big data.

Interface engineering for facile switching of bulk-strong polarization in Si-compatible vertical superlattices

Ferroelectric thin films incorporating different compositional layers have emerged as a promising approach for enhancing properties and performance of electronic devices. In recent years, superlattices utilizing various interactions between their constituent layers have been used to reveal unusual properties, such as improper ferroelectricity, charged domain walls, and negative capacitance in conventional ferroelectrics. Herein, we report a symmetry scheme based on the interface engineering in which the inherent cell-doubling symmetry allowed atomic distortions (phonons) in any vertically aligned superlattice activate novel interface couplings among atomic distortions of different symmetries and fundamentally improve the ferroelectric properties. In a materialized case, the ionic size difference between Hf4+ and Ce4+ in the HfO2/CeO2 (HCO) ferroelectric/paraelectric superlattice leads to these couplings. These couplings mitigate the phase boundary between polar and non-polar phases, and facilitate polarization switching with a remarkably low coercive field (Ec\\documentclass[12pt]{minimal} \\usepackage{amsmath} \\usepackage{wasysym} \\usepackage{amsfonts} \\usepackage{amssymb} \\usepackage{amsbsy} \\usepackage{mathrsfs} \\usepackage{upgreek} \\setlength{\\oddsidemargin}{-69pt} \\begin{document}$${E}_{c}$$\\end{document}) while preserving the original magnitude of the bulk HfO2 polarization and its scale-free ferroelectric characteristics. We show that the cell-doubled distortions present in any vertical superlattice have unique implications for designing low-voltage ferroelectric switching while retaining bulk-strong charge storing capacities in Si-compatible memory candidates.

Ferroelectric polycrystalline Bi2SiO5 thin films on Pt-covered Si substrates prepared by pulsed laser deposition combined with post-annealing

In this study, we report on the fabrication of polycrystalline thin film Bi2SiO5, a notable non-perovskite ferroelectric material. The thin films were deposited on Pt-covered Si substrates by pulsed laser deposition (PLD) at room temperature, followed by a post-annealing process in air. The as-deposited thin film was of an amorphous phase of Bi-Si-O, and turned to a polycrystalline phase of Bi2SiO5 by the post-annealing above 550°C. The influences of the post-annealing temperature on the phase preference, surface morphology, and dielectric properties of the thin films were investigated by Raman spectroscopy, X-ray diffraction (XRD), atomic force microscopy (AFM), and dielectric measurements. As a result, the optimal post-annealing temperature was determined to be 600°C, yielding a good ferroelectric polycrystalline Bi2SiO5 thin film with a relative dielectric constant of 143 and a remanent polarization (2Pr) of 7.2 μC cm−2.

Ferroelectric Thin Films and Composites Based on Polyvinylidene Fluoride and Graphene Layers: Molecular Dynamics Study

This work is devoted to the study of nanosized polymer polyvinylidene fluoride (PVDF) thin ferroelectric films (two-dimensional ferroelectrics) and their composites with graphene layers, using molecular dynamics methods to (1) study and calculate the polarization switching time depending on the electric field and film thickness, (2) study and calculate the polarization switching time depending on changes of the PVDF in PVDF-TrFE film, and (3) study the polarization switching time in PVDF under the influence of graphene layers. All calculations at each MD run step were carried out using the semi-empirical quantum method PM3. A comparison and analysis of the results of these calculations and the kinetics of polarization switching within the framework of the Landau–Ginzburg–Devonshire theory for homogeneous switching in ferroelectric polymer films is carried out. The study of the composite heterostructures of the “graphene-PVDF” type, and calculations of their polarization switching times, are presented. It is shown that replacing PVDF with PVDF-TrFE significantly changes the polarization switching times in these thin polymer films, and that introducing various graphene layers into the PVDF layered structure leads to both an increase and a decrease in the polarization switching time. It is shown that everything here depends on the position and displacement of the coercive field depending on the damping parameters of the system. These phenomena are very important for various ferroelectric coatings.

Phase-field theory study on the modulation mechanism of oxygen vacancy concentration on charged domain wall in ferroelectric thin films

This study analyzes the regulatory mechanism of oxygen vacancy concentration on tail-to-tail charged domain walls (T–T CDWs), along with the writing time, conduction current magnitude, and retention performance of through-type T–T CDWs. The research results show that the highest density and length of T–T CDWs are achieved when the oxygen vacancy concentration is 1 × 1020 cm−3. Moreover, the successful writing of through-type T–T CDWs is limited to a certain electric field range, which is controlled by oxygen vacancy concentration. An increase in the oxygen vacancy concentration leads to a decrease in the maximum and minimum threshold electric fields required for writing through-type charged domain walls. The writing time and conductivity of through-type T–T CDWs determine the information writing speed and signal strength of domain wall memories, and the oxygen vacancy concentration also plays a regulatory role in both aspects. When the oxygen vacancy concentration is 1 × 1020 cm−3, the through-type T–T CDW exhibits the fastest writing speed, requiring only 8 ns. The magnitude of the conduction current of through-type T–T CDWs is directly proportional to the oxygen vacancy concentration. The through-type T–T CDWs formed by the aggregation of oxygen vacancies exhibit excellent retention performance, making them highly promising for applications in ferroelectric domain wall memories. Our research demonstrates that oxygen vacancies have a significant regulatory effect on the morphology and current response of charged domain walls, opening up new avenues for the study of domain wall memories.

Reversible charge injection in artificially created charged domain wall region

The impact of electric field application in the charged domain wall (DW) region on the performance of DW devices remains elusive. Here, we present our observations of substantial charge injection occurring in an artificially created charged DW region. Rapid charge injection coincides with polarization switching, contributing to the transient current collected for the integration of polarization-voltage hysteresis loops. Subsequently, a gradual injection of charges persists under externally applied voltages, diffusing into the thin film from the DW region to screen the space defect dipoles and effectively suppressing the imprint field. The process of charge injection proves reversible and is notably more pronounced in aged ferroelectric thin films, as evidenced in planar BiFeO3 nanodevices where the charge injection amount is five orders of magnitude higher than charges generated from polarization switching. This work constitutes a significant contribution to understanding the intricate process of charge injection and its influence on charged DW.

Large room temperature magnetoelectric response in quasi 1–2 nanocomposite films on mica substrate

AbstractA novel quasi 1–2 type magnetoelectric (ME) nanocomposite films composted of one‐dimensional CoFe2O4 nanofibers and two‐dimensional PbZr0.2Ti0.8O3 films on flexible mica substrate have been designed and fabricated. The ME coupling effects have been greatly enhanced due to the release of the clamping effect and the high strain transfer efficiency between the large aspect ratio of the nanofibers and ferroelectric thin films. The release of the clamping effect was confirmed by reducing the thickness of the mica substrate, in which the piezoelectric coefficient and ME coupling coefficient of the nanocomposite films have been greatly boosted by the decrease in the mica thickness. A large direct ME coupling coefficient of 630 mV/(cm Oe) and a converse ME coupling coefficient of 1.43 × 10−8 s/m have been achieved in the quasi 1–2 nanocomposite film with a substrate thickness of 25 µm. Furthermore, the stain‐mediated ME coupling was revealed by magnetic field/electric field‐induced local ferroelectric/magnetic domain switching dynamics.

Improved energy storage properties through multilayer stacking of relaxor ferroelectric and antiferroelectric thin films

Abstract Multilayers of relaxor ferroelectric (Pb0.92La0.08Zr0.52Ti0.48O3) and antiferroelectric (Pb0.96La0.04Zr0.98Ti0.02O3) thin films were fabricated on Pt/Ti/SiO2/Si substrates by Chemical Solution Deposition (CSD) method. The properties of the independent relaxor ferroelectric (RFE denoted as R) and antiferroelectric (AFE denoted as A) thin films were compared with their various stack configurations made by alternatively coating the R and A layers in the patterns of R/A, R/A/R, R/A/R/A/R/A, A/R, A/R/A, and A/R/A/R/A/R. The crystallographic studies confirmed the coexistence of both RFE and AFE phases in the multilayer stacks which was further verified by electrical characterizations. The multilayer stack showed improved power density (PD), energy efficiency (η), and reduced dielectric loss compared to individual R and A films. Among all the multilayer configurations, the stack with A/R/A/R/A/R layer exhibited significant improvement in energy efficiency (94%) which is higher than the reported results so far on multilayer structures.

Reversible Optical Control of Polarization in Epitaxial Ferroelectric Thin Films.

Light is an effective tool to probe the polarization and domain distribution in ferroelectric materials passively, that is, non-invasively, for example, via optical second harmonic generation (SHG). With the emergence of oxide electronics, there is now a strong demand to expand the role of light toward active control of the polarization. In this work, optical control of the ferroelectric polarization is demonstratedin prototypical epitaxial PbZrx Ti1-x O3 (PZT)-based heterostructures. This is accomplished in three steps, using above-bandgap UV light, while tracking the response of the polarization with optical SHG. First, it is found that UV-light exposure induces a transient enhancement or suppression of the ferroelectric polarization in films with an upward- or downward-oriented polarization, respectively. This behavior is attributed to a modified charge screening driven by the separation of photoexcited charge carriers at the Schottky interface of the ferroelectric thin film. Second, by taking advantage of this optical handle on electrostatics, remanent optical poling from a pristine multi-domain into a single-domain configuration is accomplished. Third, via thermal annealing or engineered electrostatic boundary conditions, a complete reversibility of the optical poling is further achieved. Hence, this work paves the way for the all-optical control of the spontaneous polarization in ferroelectric thinfilms.

Reliable ferroelectricity down to cryogenic temperature in wake-up free Hf0.5Zr0.5O2 thin films by thermal atomic layer deposition

The performance and reliability of ferroelectric thin films at temperatures around a few Kelvin are critical for their application in cryo-electronics. In this work, TiN/Hf0.5Zr0.5O2/TiN capacitors that are free from the wake-up effect are investigated systematically from room temperature (300 K) to cryogenic temperature (30 K). We observe a consistent decrease in permittivity (ε r) and a progressive increase in coercive electric field (E c) as temperatures decrease. Our investigation reveals exceptional stability in the double remnant polarization (2P r) of our ferroelectric thin films across a wide temperature range. Specifically, at 30 K, a 2P r of 36 µC/cm2 under an applied electric field of 3.0 MV/cm is achieved. Moreover, we observed a reduced fatigue effect at 30 K in comparison to 300 K. The stable ferroelectric properties and endurance characteristics demonstrate the feasibility of utilizing HfO2 based ferroelectric thin films for cryo-electronics applications.

Phase transitions in ferroelectric ZrO2 thin films

In this work, the formation of the orthorhombic phase of ZrO2 together with the minor monoclinic phase were elucidated by X-ray diffraction and transmission electron microscopy. Moreover, oxidized W can be responsible for the formation of oxygen vacancies in the ZrO2 through oxygen scavenging. The ferroelectric properties of the W/ZrO2/W film capacitors were investigated through piezoresponse force microscopy (PFM) and polarization-voltage measurements.A second-order phase transition from the polar orthorhombic phase to the non-polar tetragonal phase was observed. Density functional theory calculations confirm our experimental results and propose that oxygen vacancies are responsible for the Curie–Weiss temperature of 130 °C, significantly lower than the theoretical value for the bulk.

Influence of interface on the domain polarization orientation in ferroelectric Hf0.5Zr0·5O2 thin films

Ferroelectric HfO2-based materials have attracted extensive attention in the research of next-generation nonvolatile memories and logic devices due to their superior scaling properties and compatibility with the CMOS process. However, forming the ferroelectric metastable phase in the thin films of a few nanometers requires clamping of the top and bottom electrodes. As a result, the interface can significantly impact domain structure and polarization, leading to imprinting effects and non-uniform space charge distribution. Here, we have demonstrated how the interface affects the ferroelectric polarization in Hf0.5Zr0·5O2 (HZO) thin films produced by ALD and the physical mechanisms behind it. We found that by regulating the quantity of oxygen vacancy content at the top and bottom interfaces of TiN/HZO/TiN ferroelectric capacitors, it is possible to achieve inversion of polarization orientation. By using a spherical aberration-corrected transmission electron microscope and first-principles calculation, we identified that the internal electric field generated by the accumulation of oxygen vacancies at an interface and the asymmetrical electrostatic energy of the interfacial T-phase layer jointly play a role in the ferroelectric polarization orientation. Our results will significantly help the interface engineering of HfO2-based ferroelectric thin films and devices.