Ferroelectric Domain Research Articles

Giant piezoelectricity of PNN-PIN-PT ceramics via domain engineering

The ferroelectric domain plays an important role in determining the piezoelectric performance of ferroelectric ceramics. Herein, LiNbO3 (LN) is used as an additive to tune the ferroelectric domain of 0.49Pb(Ni1/3Nb2/3)O3-0.2Pb(In1/2Nb1/2)O3-0.31PbTiO3 (PNN-PIN-PT) ceramics. PNN-PIN-PT-0LN ceramic exhibits the ordered tetragonal phase (90 °) domain wall and rhombohedral phase (71 ° and 109 °) domain wall. Incorporating LN into the system leads to the transformation of the majority of structured macro-domains into random micro-domains with smaller sizes, which disrupt their long-range ordered ferroelectric domains, resulting in significant piezoelectric enhancement. Compared to PNN-PIN-PT-0LN ceramics, PNN-PIN-PT-1.8LN ceramics exhibit giant piezoelectric responses with d33 = 1112 pC/N, d31 =521 pC/N, d33*=1220 pm/V (@ E = 5 kV/cm), εr = 12092. These findings shed light on a specific aspect of domain engineering in piezoelectric materials, thus contributing to a more comprehensive understanding of the underlying factors that give rise to the phenomenon of giant piezoelectricity.

Electrically‐Reconfigurable Extremely‐High Density Physical Unclonable Cryptographic Keys Based on Aurivillius Ferroelectrics

AbstractIn the era of information, emerging hardware security primitives, i.e., hardware random number generators and physically unclonable functions, hold profound promise for the establishment of exceptionally secure network information systems. Nonetheless, these potential solutions are constrained by inherent drawbacks, including the need for additional error correction circuits or algorithms, heightened susceptibility to environmental interference, and limited data density. This paper demonstrates the extremely high‐density, physical‐unclonable cryptographic keys by harnessing stochastically ferroelectric domain polarizations in Aurivillius ferroelectric material CaBi2Nb2O9 (CBNO). Ferroelectric polarization of CBNO nanodomains can serve as a robust source of physical unclonable entropy. Through the application of high‐speed voltage pulses, the inherent randomness of ferroelectric polarizations can be enhanced, thereby yielding cryptographic keys characterized by remarkable uniformity, uniqueness, and negligible environmental sensitivity. More importantly, the voltage pulse operations facilitate the configurability of the ferroelectric cryptographic keys with no correlation. An unprecedented data density of 435 Gbit µm−2 is therefore achievable with a miniaturized CBNO of less than 1 um2. Notably, the reconfigured keys successfully pass the National Institute of Standards and Technology random number tests without requiring additional post‐processing steps. Emanating from the inherent attributes of the material, these high‐density ferroelectric keys confer intrinsic advantages to information security, evincing substantial resistance to duplication or cloning.

Large electrocaloric effect and wide working area in the transition from ferroelectric to nanodomains

AbstractA large adiabatic temperature change along with a wide operating temperature region is usually required for the electrocaloric materials to fulfill their refrigeration function. In general, doping foreign ions into BaTiO3 is the frequently utilized strategy in order to obtain excellent electrocaloric materials for the practical application. In the current paper, BaTiO3 lead‐free ferroelectric ceramics were doped by Ca2+ and Sn4+ simultaneously in order to generate a coexistence state at room temperature, where ferroelectric domains and nanodomains exit. As a result, a large polarization and a wide operating temperature range were finally induced. It is found that Ba0.9Ca0.1Ti0.85Sn0.15O3 has a maximum adiabatic temperature change of 0.85 K and an excellent working temperature region (65 K, ∆T > 90% Tmax) was achieved under an electric field of 50 kV/cm. The above phenomenon indicates that the modified BaTiO3 ceramics can be a good potential electrocaloric material in the state of cross‐existence of ferroelectric domains and nanodomains.

Effects of heterovalent ions doping-induced oxygen octahedral distortion and defect chemical change on piezoelectric characteristics and thermal stability of PHT-PIN ceramics

Electromechanical devices require functional materials possessing excellent piezoelectric properties, good thermal stability, and high electromechanical coupling coefficients. To modulate the piezoelectric, dielectric, and electromechanical characteristics of 0.89Pb(Hf0.47Ti0.53)O3-0.11Pb(In1/2Nb1/2)O3 (PHT-PIN) piezoelectric ceramics, heterovalent ions of lithium (Li) and tungsten (W) were doped through a traditional solid-phase reaction approach. On the one hand, large lattice distortions caused by the doped W6+ resulted in the shortening of BO bonds while an increase in the local displacement of B-site ions. Moreover, a mismatch occurred for the oxygen octahedral dimensions, and a subsequent disruption of the long-ranged ordered ferroelectric domains was observed, which resulted in the formation of microdomains. On the other hand, the changes in the concentration of oxygen vacancy defects induced by the Li and W doping inside the ceramic were comprehensively analyzed. The decrease in the concentration of oxygen vacancies was found to be accompanied by the enhancement of piezoelectric properties of the material. Excellent comprehensive performance (piezoelectric coefficient d33 = 655 pC N−1, Curie temperature Tc = 321.1 °C, dielectric constantεr = 3352.31, electromechanical coupling coefficient kp = 0.67, and residual polarization strength Pr = 55 μC cm−2) was obtained for 0.2 mol % doping amount of Li+ and W6+ ions. This work, therefore, proposes a novel strategy for the origin of piezoelectric properties and inspires doping of other heterovalent ions to improve the piezoelectric properties of ceramics. It further promotes the development of Pb-based piezoelectric ceramics for electromechanical devices that can efficiently operate under high-temperature environments.

Evaluating the optoelectronic properties of individual CsPbBr3 microcrystals by electric AFM techniques

All-inorganic perovskite materials are attracting the attention of researchers owing to the good performance that they exhibit in optoelectronic device applications. In particular, cesium lead halide single crystals are of interest for their electric conductivity. However, the conductive properties of these materials are still far from being fully understood. In this work, we used several scanning probe microscopy techniques to investigate different properties of CsPbBr3 single crystals, namely their topography, electric conductivity, electric surface potential and ferroelectricity. We observed heterogeneity in conductance and work function of the different facets by using conductive atomic force microscopy and Kelvin probe force microscopy measurements. Additionally, piezo-response force microscopy was carried out to gain insight on the origin of the hysteresis in our microcrystals. Our results show the absence of ferroelectric domains and we attribute the I–V hysteresis to ionic migration within the crystal.

Conducting atomic force microscopy studies on domain wall currents of Bi5Ti3FeO15 nanodots fabricated by anodic aluminum oxide nanotemplate and sol-gel process.

We investigated the local current characteristics of Bi5Ti3FeO15 (BTFO) nanodots on Nb-doped SrTiO3 substrates affected by their ferroelectric domain structures and domain walls. The BTFO nanodots with a diameter of about 50 nm were fabricated by anodic aluminum oxide nanotemplates and a BTFO sol-gel process. Based on a piezoresponse force microscope, it was confirmed that domain walls were formed in the ferroelectric domain structures of the epitaxial BTFO nanodots. Current changes due to ferroelectric tunneling junctions according to ferroelectric polarizations in epitaxial BTFO nanodots were confirmed by conduction atomic force microscopy. In particular, the domain walls formed in the epitaxial BTFO nanodots formed high currents compared to the currents in ferroelectric tunneling junctions due to polarizations. RESEARCH HIGHLIGHTS: Ferroelectric Bi5Ti3FeO15 nanodots with a diameter of 50 nm. Ferroelectric domain structures observed with piezoresponse force microscopy. High domain wall currents observed at domain boundaries observed with conducting atomic force microscopy.

Optimized energy storage properties of Bi0.5Na0.5TiO3-based lead-free ceramics by composition regulation

To meet the demand for miniaturization and integration of electronic and electrical equipments, developing dielectric capacitors with excellent energy storage properties is of utmost importance. Bi0.5Na0.5TiO3-based ceramics have been investigated extensively for potential energy storage applications. However, its low breakdown strength Eb and high remnant polarization Pr limit the energy storage density and efficiency (η). Therefore, we explored a synergistic design strategy of domain control and grain size adjustment via La doping to successfully synthesize 0.8Bi0.5Na0.5TiO3-0.2NaNbO3-xLa2O3 (0.8BNT-0.2NN-xLa2O3) ceramics with superior energy storage properties to overcome above issues. It shows that the composition regulation by antiferroelectric NaNbO3 results in improved disrupted long rang order ferroelectric domain structure, effectively promoting the formation of polar nanoregions, subsequently weakening Pr and enhancing relaxation behavior. The introduction of antiferroelectric NaNbO3 effectively improves the η of the system. Moreover, the grain size is decreased and densification is enhanced after La tailoring, which is beneficial for the Eb and recyclable energy storage density (Wrec). Finally, a high Wrec of 4.40 ± 0.20 J/cm3 and η of 80.1 ± 2.1% at 450 kV/cm are obtained in 0.8BNT-0.2NN-0.07La2O3 ceramic. Besides, the sample demonstrates admirable temperature stability (25–175 °C) and frequency stability (10–100 Hz). Simultaneously, it displays stable discharge energy density, rapid discharge time of 0.36 μs, and good fatigue endurance (105 cycles). The results offer useful guidance for the design of novel ceramic capacitors with comprehensive energy storage performance.

Electrically controllable chiral phonons in ferroelectric materials

Chiral phonons have attracted increasing attention, as they play important roles in many different systems and processes. However, a method to control phonon chirality by external fields is still lacking. Here, we propose that in displacement-type ferroelectric materials, an external electric field can reverse the chirality of chiral phonons via ferroelectric switching. Using first-principles calculations, we demonstrate this point in the well-known two-dimensional ferroelectric In2Se3. This reversal may lead to a number of electrically switchable phenomena, such as chiral phonon induced magnetization, the phonon Hall effect, and possible topological interface chiral phonon modes at ferroelectric domain boundaries. Our work offers a way to control chiral phonons, which could be useful for the design and application of thermal or information devices based on them.

Influence of oxygen vacancies on the domain wall stability in BiFeO3

AbstractOxygen vacancy is the most common type of point defects in functional oxides, and it is known to have profound influence on their properties. This is particularly true for ferroelectric oxides since their interaction with ferroelectric polarization often dictates the ferroelectric responses. Here, we study the influence of the concentration of oxygen vacancies on the stability of ferroelectric domain walls (DWs) in BiFeO3, a material with a relatively narrow bandgap among all perovskite oxides, which enables strong interactions among electronic charge carriers, oxygen vacancies, and ferroelectric domains. It is found that the electronic charge carriers in the absence of oxygen vacancies have essentially no influence on the spatial polarization distribution of the DWs due to their low concentrations. Upon increasing the concentration of oxygen vacancies, charge‐neutral DWs with an originally symmetric polarization distribution symmetric around the center of the wall can develop a strong asymmetry of the polarization field, which is mediated by the electrostatic interaction between polarization and electrons from the ionization of oxygen vacancies. Strongly charged head‐to‐head DWs that are unstable without oxygen vacancies can be energetically stabilized in the off‐stoichiometric BiFeO3−δ with δ ∼ 0.02 where ionization of oxygen vacancies provides sufficient free electrons to compensate the bound charge at the wall. Our results delineate the electrostatic coupling of the ionic defects and the associated free electronic charge carriers with the bound charge in the vicinity of neutral and charged DWs in perovskite ferroelectrics.

Perspectives and progress on wurtzite ferroelectrics: Synthesis, characterization, theory, and device applications

Wurtzite ferroelectrics are an emerging material class that expands the functionality and application space of wide bandgap semiconductors. Promising physical properties of binary wurtzite semiconductors include a large, reorientable spontaneous polarization, direct band gaps that span from the infrared to ultraviolet, large thermal conductivities and acoustic wave velocities, high mobility electron and hole channels, and low optical losses. The ability to reverse the polarization in ternary wurtzite semiconductors at room temperature enables memory and analog type functionality and quasi-phase matching in optical devices and boosts the ecosystem of wurtzite semiconductors, provided the appropriate combination of properties can be achieved for any given application. In this article, advances in the design, synthesis, and characterization of wurtzite ferroelectric materials and devices are discussed. Highlights include: the direct and quantitative observation of polarization reversal of ∼135 μC/cm2 charge in Al1−xBxN via electron microscopy, Al1−xBxN ferroelectric domain patterns poled down to 400 nm in width via scanning probe microscopy, and full polarization retention after over 1000 h of 200 °C baking and a 2× enhancement relative to ZnO in the nonlinear optical response of Zn1−xMgxO. The main tradeoffs, challenges, and opportunities in thin film deposition, heterostructure design and characterization, and device fabrication are overviewed.

Direct imaging of the magnetoelectric coupling in multiferroic BaTiO3/La0.9Ba0.1MnO3

We report the direct imaging of the magnetic response of a 4.8 nm La0.9Ba0.1MnO3 film to the voltage applied across a 5 nm BaTiO3 film in a BaTiO3/La0.9Ba0.1MnO3 multiferroic heterostructure using x-ray photoemission electron microscopy (XPEEM). Specifically, we have written square ferroelectric domains on the BaTiO3 layer with an atomic force microscope in contact mode and imaged the corresponding magnetic contrast through the x-ray circular dichroic effect at the Mn L-edge with high spatial lateral resolution using XPEEM. We find a sudden decrease in the magnetic contrast for positive writing voltages above +6 V associated with the switching of the ferroelectric polarization of the BaTiO3, consistent with the presence of a magnetoelectric effect through changes in the hole carrier density at the BaTiO3/La0.9Ba0.1MnO3 interface. Temperature-dependent measurements show a decrease in the Curie temperature and magnetic moment in the areas where a positive voltage above +6 V was applied, corresponding to the hole depletion state and suggesting the onset of a spin-canted state of bulk La0.9Ba0.1MnO3. Our results are the first direct imaging of magnetoelectric coupling in such multiferroic heterostructure.

Non‐Destructive Tomographic Nanoscale Imaging of Ferroelectric Domain Walls

AbstractExtraordinary physical properties arise at polar interfaces in oxide materials, including the emergence of 2D electron gases, sheet‐superconductivity, and multiferroicity. A special type of polar interface is ferroelectric domain walls, where electronic reconstruction phenomena can be driven by bound charges. Great progress has been achieved in the characterization of such domain walls and, over the last decade, their potential for next‐generation nanotechnology has become clear. Established tomography techniques, however, are either destructive or offer insufficient spatial resolution, creating a pressing demand for 3D imaging compatible with future fabrication processes. Here, non‐destructive tomographic imaging of ferroelectric domain walls is demonstrated using secondary electrons. Utilizing conventional scanning electron microscopy (SEM), the position, orientation, and charge state of hidden domain walls are reconstructed at distances up to several hundreds of nanometers away from the surface. A mathematical model is derived that links the SEM intensity variations at the surface to the local domain wall properties, enabling non‐destructive tomography with good noise tolerance on the timescale of seconds. The SEM‐based approach facilitates high‐throughput screening of materials with functional domain walls and domain‐wall‐based devices, which is essential for monitoring during the production of device architectures and quality control in real‐time.

Back‐End‐of‐Line Integration of Synaptic Weights using HfO2/ZrO2 Nanolaminates

AbstractIn artificial neural networks, the “synaptic weights” connecting the neurons are adjusted during the training. Beyond silicon, functionalizing the back‐end‐of‐line (BEOL) of CMOS circuits with novel materials is a key enabler for deploying neural network accelerators. The hardware implementation of the synaptic weights requires linear and reprogrammable resistive elements. In ferroelectric tunnel junctions, the resistance is programmed by controlling the configuration of the ferroelectric domains with electrical pulses. From ferroelectric HfZrO4 to HfO2–ZrO2 nanolaminates (NL), the crystallization temperature lowers below the upper limit of 400 °C required for CMOS BEOL. The device footprint is reduced, and the maximum‐to‐minimum conductance ratio increases from 7 to 32. Operated with pulses in the ultra‐fast (20 ns) and biological (500 µs) timescales, the synaptic plasticity exhibits several regimes. Dynamic hysteresis mode characterization after up to 1011 switching cycles indicates the coexistence of ferroelectric and non‐ferroelectric effects such as defect rearrangement. Temperature‐dependent transport measurements in the Ohmic (linear) regime support these conclusions. Multi‐level resistive switching is achieved in HfO2–ZrO2 NL co‐integrated to CMOS in the BEOL. 1T‐1R operation is demonstrated, paving the way for hardware implementation of synaptic weights for in‐memory neuromorphic computing.

Effect of annealing conditions on surface morphology and ferroelectric domain structures of BiFeO3 thin films

Ferroelectric materials are widely used in the applications of electronic devices due to their robust spontaneous polarization. The surface roughness of ferroelectric thin films, which is closely related to the morphology, can play an important role in determining the ferroelectric domain structures. In this work, we have investigated the influence of annealing conditions on the surface morphology of epitaxial BiFeO3 and SrRuO3 thin films prepared by pulsed laser deposition on SrTiO3 (001) substrates. It is found that the morphology of the thin films is sensitive to the annealing time and cooling rate, and the corresponding surface roughness decreases with increasing annealing time and decreasing cooling rate. In addition, the ferroelectric domain structures of BiFeO3 films have been investigated by piezoelectric force microscopy, which shows a significant improvement in domain size and reverse piezoelectric response in the thin films with decreasing surface roughness. This work provides a simple way to predict and improve the ferroelectric domain structures by in situ annealing.

Poling-assisted hydrofluoric acid wet etching of thin-film lithium niobate.

Thin-film lithium niobate (TFLN) has been extensively investigated for a wide range of applications due to continuous advancements in its fabrication methods. The recent emergence of high-fidelity ferroelectric domain poling of TFLN provides an opportunity for achieving a precise pattern control of ferroelectric domains and a subsequent pattern transfer to the TFLN layer using hydrofluoric acid (HF). In this work, we present, to the best of our knowledge, the first demonstration of z-cut TFLN microdisks using a poling-assisted HF wet etching approach. By applying intense electric fields, we are able to induce a domain inversion in the TFLN with a designed microdisk pattern. A HF solution is subsequently utilized to transfer the inverted domain pattern to the TFLN layer with the selective etching of -z LN, ultimately revealing the microdisks.

Integration of epitaxial LiNbO3 thin films with silicon technology

Development of bulk acoustic wave filters with ultra-wide pass bands and operating at high frequencies for 5th and 6th generation telecommunication applications and micro-scale actuators, energy harvesters and sensors requires lead-free piezoelectric thin films with high electromechanical coupling and compatible with Si technology. In this paper, the epitaxial growth of 36°Y-X and 30°X-Y LiNbO3 films by direct liquid injection chemical vapour deposition on Si substrates by using epitaxial SrTiO3 layers, grown by molecular beam epitaxy, has been demonstrated. The stability of the interfaces and chemical interactions between SrTiO3, LiNbO3 and Si were studied experimentally and by thermodynamical calculations. The experimental conditions for pure 36°Y-X orientation growth have been optimized. The piezoelectricity of epitaxial 36°Y-X LiNbO3/SrTiO3/Si films was confirmed by means of piezoelectric force microscopy measurements and the ferroelectric domain inversion was attained at 85 kV.cm−1 as expected for the nearly stoichiometric LiNbO3. According to the theoretical calculations, 36°Y-X LiNbO3 films on Si could offer an electromechanical coupling of 24.4% for thickness extension excitation of bulk acoustic waves and a comparable figure of merit of actuators and vibrational energy harvesters to that of standard PbZr1−x Ti x O3 films.

Van der Waals Epitaxial Growth of One-Unit-Cell-Thick Ferroelectric CuCrS2 Nanosheets.

Ferroelectric two-dimensional (2D) materials with a high transition temperature are highly desirable for new physics and next-generation memory electronics. However, the long-range polar order of ferroelectrics will barely persist when the thickness reaches the nanoscale. In this work, we synthesized 2D CuCrS2 nanosheets with thicknesses down to one unit cell via van der Waals epitaxy in a chemical vapor deposition system. A combination of transmission electron microscopy, second-harmonic generation, and Raman spectroscopy measurements confirms the R3m space group and noncentrosymmetric structure. Switchable ferroelectric domains and obvious ferroelectric hysteresis loops were created and visualized by piezoresponse force microscopy. Theoretical calculation helps us understand the mechanism of ferroelectric switching in CuCrS2 nanosheets. Finally, we fabricated a ferroelectric memory device that achieves an on/off ratio of ∼102 and remains stable after 2000 s, indicating its applicability in novel nanoelectronics. Overall, 2D CuCrS2 nanosheets exhibit excellent ferroelectric properties at the nanoscale, showing great promise for next-generation devices.

Characterization of ferroelectric domains in magnetite (Fe3O4)

Magnetite has long been investigated across many disciplines due to the interplay between its ferroic order parameters, namely, its ferrimagnetism, ferroelasticity, and ferroelectricity. Despite this, the experimental difficulty in measuring low temperature real space images of the ferroelectric domains has meant that the local behavior of ferroelectric domains emergent below the ∼38 K phase transition have yet to be realized. This work presents real space images of the ferroelectric domains and uses piezoresponse force microscopy as a function of temperature to probe the onset of piezoelectricity and ferroelectricity across the 38 K transition.

Nanoscopic spin-wave channeling along programmable magnetic domain walls in a CoFeB/BaTiO3 multiferroic heterostructure

We report a micromagnetic study on spin-wave propagation along magnetic domain walls in a ferromagnetic/ferroelectric bilayer. In our system, strain coupling between the two ferroic materials and inverse magnetostriction produce a fully correlated domain pattern wherein straight and narrow ferroelectric domain walls pin the magnetic domain walls. Consequently, an external magnetic field does tailor the spin structure of the magnetic domain walls instead of moving them. We use experimental parameters from a previously studied CoFeB/BaTiO3 material system to investigate the potential of artificial multiferroics for programmable nanoscopic spin-wave channeling. We show that spin waves are transported along the pinned magnetic domain walls at zero magnetic field and low frequency due to a local demagnetizing field. Further, switching of the domain wall spin structure from a head-to-tail to a head-to-head configuration abruptly changes the propagating spin-wave mode. We study the effect of magnetic field strength on the localized modes and discuss reversible control of spin-wave channeling via electric-field-driven magnetic domain wall motion. Nanoscopic guiding of propagating spin waves by an electric field, in combination with positional robustness to and mode programming by an external magnetic field, offers prospects for low-power and reconfigurable domain-wall-based magnonic devices.

Realizing Super‐High Piezoelectricity and Excellent Fatigue Resistance in Domain‐Engineered Bismuth Titanate Ferroelectrics

AbstractBismuth titanate (BIT) is widely known as one of the most prospective lead‐free ferroelectric and piezoelectric materials in advanced high‐temperature sensing applications. Despite significant advances in developing BIT ferroelectrics, it still faces major scientific and engineering challenges in realizing super‐high performance to meet next‐generation high‐sensitivity and light‐weight applications. Here, a novel ferroelectric domain‐engineered BIT ceramic system is conceived that exhibits super‐high piezoelectric coefficient (d33 = 38.5 pC N−1) and inverse piezoelectric coefficient (d33* = 46.7 pm V−1) at low electric field as well as excellent fatigue resistance (stable up to 107 cycles). The results reveal that the introduction of high‐density layered (001)‐type 180° domain walls with flexible polarization rotation features and the formation of small‐size multi‐domain states with low energy barriers are mainly responsible for the excellent electrical performance. To the best of knowledge, it is the first time to reveal such intriguing domain structures in BIT ceramics in detail, especially from the atomic‐scale perspective by using atomic number (Z)‐contrast imaging in combination with atomic‐resolution polarization mapping. It is believed that this breakthrough conduces to comprehensively understand structural features of ferroelectric domains in BIT ceramics, and also opens a window for future developments of super‐high performance in bismuth layer‐structured ferroelectrics via domain engineering.