Ferroelectric Oxides Research Articles

Scalable Synthesis of High-Quality Ultrathin Ferroelectric Magnesium Molybdenum Oxide.

The development of ultrathin, stable ferroelectric materials is crucial for advancing high-density, low-power electronic devices. Nonetheless, ultrathin ferroelectric materials are rare due to the critical size effect. Here, a novel ferroelectric material, magnesium molybdenum oxide (Mg2Mo3O8) is presented. High-quality ultrathin Mg2Mo3O8 crystals are synthesized using chemical vapor deposition (CVD). Ultrathin Mg2Mo3O8 has a wide bandgap (≈4.4eV) and nonlinear optical response. Mg2Mo3O8 crystals of varying thicknesses exhibit out-of-plane ferroelectric properties at room temperature, with ferroelectricity retained even at a 2nm thickness. The Mg2Mo3O8 exhibits a relatively large remanent polarization ranging from 33 to 52µCcm- 2, which is tunable by changing its thickness. Notably, Mg2Mo3O8 possesses a high Curie temperature (>980°C) across various thicknesses. Moreover, the as-grown Mg2Mo3O8 crystals display remarkable stability under harsh environments. This work introduces nolanites-type crystal into ultrathin ferroelectrics. The scalable synthesis of stable ultrathin ferroelectric Mg2Mo3O8 expands the scope of ferroelectric materials and may prosper applications of ferroelectrics.

Pressure-dependent phase transitions in hybrid improper ferroelectric Ruddlesden-Popper oxides

Pressure-dependent phase transitions in hybrid improper ferroelectric Ruddlesden-Popper oxides

Remote epitaxy-based atmospherically stable hybrid graphene template for fast and versatile transfer of complex ferroelectric oxides onto Si

Heterogenous integration of complex epitaxial oxides onto Si and other target substrates is recently gaining traction. One of the popular methods involves growing a water-soluble and highly reactive sacrificial buffer layer, such as Sr3Al2O6 (SAO), at the interface and a functional oxide on top of this. To improve the versatility of layer transfer techniques, it is desired to utilize stable (less reactive) sacrificial layers without compromising on the transfer rates. In this study, we utilized a combination of chemical vapor deposited (CVD) graphene as a 2D material at the interface and pulsed laser deposited (PLD) water-soluble SrVO3 (SVO) as a sacrificial buffer layer. We then exploit the well-known enhancement of liquid diffusivities by monolayer graphene to enhance the dissolution rate of SVO over ten times without compromising its atmospheric stability. We demonstrate the versatility of our hybrid- graphene-SVO- template by growing ferroelectric BaTiO3 (BTO) via PLD and Pb(Zr, Ti)O3 (PZT) via Chemical Solution Deposition (CSD) technique and transferring them onto the target substrates and establishing their ferroelectric properties. Our hybrid templates allow for the realization of the potential of complex oxides in a plethora of device applications for MEMS, electro-optics, and flexible electronics.

Enhanced ferroelectric photovoltaic performance of Bi2FeCrO6 thin films for neuromorphic computing applications

Nowadays, ferroelectric photovoltaic synapses have attracted great attention due to its polarization controllable and self-powered features. However, the large bandgaps of ferroelectric oxide materials limit its application. This study focuses on the enhancement of ferroelectric photovoltaic properties and the synaptic application of Bi2FeCrO6 (BFCO) device. It is found that the bandgap of BFCO can be modulated by Cr alloying, which causes its photovoltaic effect in the visible region to exceed that of BiFeO3 (BFO) significantly. The short-circuit current density (JSC) of BFCO device in the visible region increases by about 100 times than that of BFO. Furthermore, the polarization modulation and multi-states response are demonstrated by an external electric field. For BFCO ferroelectric photovoltaic synapse, long-term potentiation/depression (LTP/LTD) measurements show an excellent synaptic plasticity of the polarization modulation. The simulated image recognition rate using the MNIST dataset reaches a high accuracy of 96.06%. This work has expanded the potential application of ferroelectric photovoltaic synapse in the visible region.

Perovskite‐Oxide‐Based Ferroelectric Synapses Integrated on Silicon

AbstractPerovskite‐oxide‐based ferroelectric tunnel junctions (FTJs) hold great potential for applications in non‐volatile memory and neuromorphic computing due to their unique properties. However, the challenges in synthesizing high crystalline quality perovskite oxides directly on silicon wafer limit the applications of these FTJs in conventional Si‐based integrated circuits, let alone the neural networks. Herein, perovskite oxide FTJs with an ON/OFF ratio up to 1.2×106, writing/erasing speed down to 1 nanosecond, and cycling endurance (>106) are achieved by integrating ultrathin freestanding ferroelectric perovskite oxide membranes directly on silicon wafers using a wet‐transfer method. Moreover, synapses based on these FTJs exhibit long‐term plasticity. For handwritten digits recognition task, the convolutional neural network (CNN) simulation is implemented achieving a recognition accuracy up to 98.9% based on the experimental performance, close to the result of 99.2% by software‐floating‐point‐based CNN. This work sheds light on the integration of ferroelectric perovskite oxides directly on silicon for high‐performance FTJ‐based non‐volatile memory and synaptic devices.

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.

Probing the effect of LaFeO3 on the structural, electrical, and dielectric properties of Sr0.8Sn0.2Bi2Nb2O9 processed through solid state route method

SrBi2Nb2O9 belongs to the class of Aurivillius layered ferroelectric oxide materials and this article offers a suitable method for understanding the structural and electrical properties of this class material for industrial application. With this aim we have synthesized LaFeO3 (LFO) doped Sr0.8Sn0.2Bi2Nb2O9 (SBN) novel ceramic by solid state route using ball milling in an ethanol medium for 20 h with 200 rpm, followed by single-step microwave sintering. For better phase formation, the obtained powders are compressed into cylindrical pellets and fired at 1000 °C for 5 h. The sample was critically analyzed using powder X-ray diffraction data confirming the distorted perovskite structure. The dielectric properties were studied in a frequency range of 10 Hz to 2 MHz at different temperatures revealing many exciting results. Further analyzing the impedance spectroscopy gives an idea about the contribution of different electrically dynamic regions in different conduction processes.

Superflexible and Stretchable Ferroelectric Memory on a Biocompatible Platform

AbstractNext‐generation flexible electronics for healthcare applications require biocompatible flexible non‐volatile memory for data storage. Ultra‐thin ferroelectric hafnium oxide films offer great potential for flexible memories due to their potential flexibility and perfect compatibility with modern technologies. This study presents ultra‐flexible and stretchable memory devices based on 10‐nm‐thick Hf0.5Zr0.5O2 film fabricated by an innovative technology involving encapsulation of the devices in a biocompatible organic package. They exhibit high memory functionality (remanent polarization of 27 µC cm−2) and withstand extreme mechanical conditions, including folding in half, multiple bending up to 150 000 bending cycles as well as tension with loads up to 1.5 kg. Further, flexible devices are employed as a platform to elucidate the fundamental role of mechanical stress in ferroelectricity of hafnia both experimentally and theoretically. Direct in situ experiment demonstrates that in‐plane tension causes changes in spontaneous polarization, coercive voltage, permittivity, and conductivity. First‐principle calculations explain the role of mechanical stress in ferroelectric and dielectric properties of hafnia. In applications, this work establishes a foundation for the implementation of biocompatible, high‐performance flexible ferroelectric memory, and in the field of ferroelectric materials fundamentals, it provides insight into the critical role of the residual mechanical stress that is inevitably present in thin films.

Impacts to FeRAM Design Arising From Interfacial Dielectric Layers and Wake-Up Modulation in Ferroelectric Hafnium Zirconium Oxide.

As ferroelectric hafnium zirconium oxide (HZO) becomes more widely utilized in ferroelectric microelectronics, integration impacts of intentional and nonintentional dielectric interfaces and their effects upon the ferroelectric film wake-up (WU) and circuit parameters become important to understand. In this work, the effect of the addition of a linear dielectric aluminum oxide, Al2O3, below a ferroelectric Hf0.58Zr0.42O2 film in a capacitor structure for FeRAM applications with niobium nitride (NbN) electrodes was measured. Depolarization fields resulting from the linear dielectric is observed to induce a reduction of the remanent polarization of the ferroelectric. Addition of the aluminum oxide also impacts the WU of the HZO with respect to the cycling voltage applied. Intricately linked to the design of a FeRAM 1C/1T cell, the metal-ferroelectric-insulator-metal (MFIM) devices are observed to significantly shift charge related to the read states based on aluminum oxide thickness and WU cycling voltage. A 33% reduction in the separation of read states are measured, which complicates how a memory cell is designed and illustrates the importance of clean interfaces in devices.

Nano-positive up negative down in binary oxide ferroelectrics

Ferroelectric HfO2 and ZrO2-based materials are promising candidates for next-generation ferroelectric devices, but their characterization is challenging due to complex factors such as crystal phases, degradation mechanisms, and local inhomogeneities. In this work, we propose a novel nanosized positive-up-negative-down (PUND) method to assess the ferroelectric response of doped-HfO2. This method is based on actual current probing and is immune to most electrostatic artifacts that plague other electrical atomic force microscopy (AFM) techniques. We demonstrate the PUND method’s ability to induce ferroelectric switching in Si-doped HfO2 and investigate the distinctive PUND response obtained for individual grains. We also extract the polarization charge based on a direct estimate of the tip–sample contact area. The proposed PUND method is a significant innovation as it is a method to combine the high spatial resolution of AFM with the immunity to electrostatic artifacts of current probing. This makes it a powerful tool for studying ferroelectric materials at the nanoscale, where local inhomogeneities and other effects can have a significant impact on their behavior. The PUND method is also notable for its ability to extract polarization charge based on a direct estimate of the tip–sample contact area. This is a significant improvement over previous methods, which often relied on indirect or approximate estimates of the contact area. Overall, the PUND method is a novel and innovative technique that offers significant advantages for the characterization of ferroelectric materials at the nanoscale. It is expected to have a major impact on the research and development of next-generation ferroelectric devices.

Electrical characterization of Sn modified barium bismuth zirconate

BaBi4Sn4O15, a Sn-modified ceramic sample of layered ferroelectric oxide family, is developed using a high-temperature mixed oxide route after firing for calcination at 810 °C for 6 h in steps of 50 °C starting from 600 °C. An introductory XRD study of the compound displays the development of the new orthorhombic structured single-phase compound at atmospheric conditions. The electrical behaviors of the compound are investigated in a wide temperature span (30–500 °C) and frequencies ranging from 0.1 kHz to 1 MHz using an impedance analyzer. Dielectric behavior informs that the compound has a phase transition from Ferro to Paraelectric at 370 °C, which is well above room temperature. The impact of temperature and frequency on complex immittance parameters (impedance and modulus) is analyzed using an LCR meter in a broad temperature & frequency span. The electrical properties confirm; (a) the existence of semiconductor-like NTCR (negative temperature coefficients of resistance) behavior, (b) the evidence of the electric relaxation process as a function of temperature, (c) the existence of electric relaxation ascribed to the simultaneous contribution of bulk & bulk interfaces to the electrical behavior, and (d) presence of the non-Debye type relaxation phenomena. The frequency-dependent conductivity follows Jonscher’s universal power law.

Assessment of the Biosensing Capabilities of SiGe Heterojunction Negative Capacitance-Vertical Tunnel Field-Effect Transistor.

In this study, a comparison of the negative capacitance vertical tunnel field-effect transistor (NC-VTFET) and VTFET for biosensing applications was conducted. Dielectrically modulated TFET demonstrates better sensitivity than the traditional metal oxide field effect transistor as a biosensor in label-free biosensing applications. The TFET biosensor, however, has much room for advancement by enhancing its DC characteristics. This research addresses the impact of ferroelectric gate oxide for integration of negative capacitance (NC) effect with the SiGe heterojunction pocket at the source-channel junction to enhance performance for biosensor applications. By putting the NC layer over SiO2, the channel voltage increases with decreased subthreshold slope and OFF current, thereby creating an NC effect. Because SiGe has a narrow band gap, pocket doping of SiGe near the source channel junction will increase the concentration of charge carriers, improving the band-to-band tunneling. In order to aid in the integration of biomolecules and to modulate band-to-band tunneling based on charge density (qf), dielectric constant (k), temperature, and cavity length, a cavity is additionally inserted above the source channel junction and underneath the NC layer, near to SiO2. These values were compared with and without the incorporation of NC layer with respect to various electrical properties such as drain current (Id), sensitivity, and electric field (E). According to the findings, labeled and label-free biosensors' sensitivity may be increased by incorporating the NC effect into VTFET biosensors.

Three-Dimensional Visualization of Oxygen-Vacancy Migration and Redistribution in Ca-Substituted BiFeO3.

Ionic movement has received renewed attention in recent years, particularly in the field of ferroelectric oxides, since it is intrinsically linked to chemical reaction kinetics and ferroelectric phase stability. The associated surface electrochemical processes coupled local ionic transport with an applied electric bias, exhibiting very high ionic mobility at room temperature based on a simple electrostatics scenario. However, few studies have focused on the applied-polarity dependence of ionic migration with directly visualized maps. Here, we use incorporated experiments of conductive scanning probe microscopy and time-of-flight secondary ion mass spectrometry to investigate oxygen ionic migration and cation redistribution in ionic oxides. The local concentrations of oxygen vacancies and other cation species are visualized by three-dimensional mappings, indicating that oxygen vacancies tend to be ejected toward the surface. An accumulation of oxygen vacancies and ionic redistribution strongly depend on tip polarity, thus corroborating their role in the electrochemical process. This work illustrates the interplay between ionic kinetics and electric switching.

Comparison of carrier doping in ZnSnO3 and ZnTiO3 from first principles.

Ferroelectric materials have attracted increasing attention due to their rich properties. Unlike perovskite ferroelectric oxides, in the LiNbO3-type ferroelectric oxides of ABO3, ferroelectrically active cations are not necessary. While the effects of carrier doping on perovskite ferroelectric oxides have been extensively studied, the studies on LiNbO3-type ferroelectric oxides are rare. We consider two LiNbO3-type ferroelectric oxides ZnSnO3 and ZnTiO3, where the former has no ferroelectrically active cation and the latter has ferroelectrically active cation Ti4+, and study the effect of carrier doping by performing first-principles calculations. Comparison results indicate that the B-site cation has significant effects on the polar distortion in LN-type ferroelectrics. Our studies show that LN-type materials can maintain the coexistence of ferroelectricity and conductance over a very wide range of concentrations. The polar displacement is even enhanced under hole doping. More importantly, ZnSnO3 can be doped by electrons up to a high level to realize the conducting ferroelectrics of high mobility due to its isolated s conduction band.

Oxygen vacancies stabilized 180° charged domain walls in ferroelectric hafnium oxide

Ferroelectric domain walls (DWs) are spatial interfaces separating domains with distinct polarization orientations. Among these DWs, some can carry bound charges and display metallic-like conductivity. The feature is highly of interest for future nanoelectronics. However, the inherent instability of charged domain walls (CDWs) has posed a critical challenge for their experimental exploration. This Letter reports the head-to-head (HH) and tail-to-tail (TT) 180° CDWs within the context of ferroelectric hafnium oxide. We proposed that oxygen vacancy is a crucial factor stabilizing the periodic CDWs. Through meticulous first-principles calculations, we elaborated on the intricate properties of these CDWs, including their polarization profiles, and potential and charge distributions. Furthermore, we calculated the energy barrier for layer-by-layer propagation of a HH wall and carefully discussed the migration of a TT wall with oxygen vacancy. Our study can shed more light onto the characteristics of CDWs and their implications to hafnia-based ferroelectric devices.

A giant intrinsic photovoltaic effect in atomically thin ReS2.

The photovoltaic (PV) effect in non-centrosymmetric materials consisting of a single component under homogeneous illumination can exceed the fundamental Shockley-Queisser limit compared to the traditional p-n junctions. Two-dimensional (2D) materials with a reduced dimensionality and smaller bandgap were predicated to be better candidates for the PV effect with high efficiency exceeding that of traditional ferroelectric perovskite oxides. Here, we report the giant intrinsic PV effect in atomically thin rhenium disulfide (ReS2) with centrosymmetry breaking. In graphene/ReS2/graphene sandwich structures, significant short-circuit currents (Isc) were observed with illumination over the visible spectral range, presenting the highest responsivity (110 mA W-1) and external quantum efficiency (25.7%) among those reported PV effects in 2D materials. This giant PV effect could be ascribed to the spontaneous-polarization induced depolarization field in even-number-layered ReS2 flakes benefiting from the distorted 1T lattice structure. Our results provide a new potential candidate material for the development of novel high-efficiency, miniaturized and easily integrated photodetectors and solar cells.

Permissible domain walls in monoclinic MAB ferroelectric phases.

The concept of monoclinic ferroelectric phases has been extensively used over recent decades for the understanding of crystallographic structures of ferroelectric materials. Monoclinic phases have been actively invoked to describe the phase boundaries such as the so-called morphotropic phase boundary in functional perovskite oxides. These phases are believed to play a major role in the enhancement of such functional properties as dielectricity and electromechanical coupling through rotation of spontaneous polarization and/or modification of the rich domain microstructures. Unfortunately, such microstructures remain poorly understood due to the complexity of the subject. The goal of this work is to formulate the geometrical laws behind the monoclinic domain microstructures. Specifically, the result of previous work [Gorfman et al. (2022). Acta Cryst. A78, 158-171] is implemented to catalog and outline some properties of permissible domain walls that connect `strain' domains with monoclinic (MA/MB type) symmetry, occurring in ferroelectric perovskite oxides. The term `permissible' [Fousek & Janovec (1969). J. Appl. Phys. 40, 135-142] pertains to the domain walls connecting a pair of `strain' domains without a lattice mismatch. It was found that 12 monoclinic domains may form pairs connected along 84 types of permissible domain walls. These contain 48 domain walls with fixed Miller indices (known as W-walls) and 36 domain walls whose Miller indices may change when free lattice parameters change as well (known as S-walls). Simple and intuitive analytical expressions are provided that describe the orientation of these domain walls, the matrices of transformation between crystallographic basis vectors and, most importantly, the separation between Bragg peaks, diffracted from each of the 84 pairs of domains, connected along a permissible domain wall. It is shown that the orientation of a domain wall may be described by the specific combination of the monoclinic distortion parameters r = [2/(γ - α)][(c/a) - 1], f = (π - 2γ)/(π - 2α) and p = [2/(π - α - γ)] [(c/a) - 1]. The results of this work will enhance understanding and facilitate investigation (e.g. using single-crystal X-ray diffraction) of complex monoclinic domain microstructures in both crystals and thin films.

Ultrahigh-speed absolute temperature sensing using ferroelectric HfO2 enabled by transient negative differential capacitance.

Conventional ferroelectric polarization-driven temperature sensors, like pyroelectric sensors, often face challenges such as slow response times, limited compatibility with conventional nanoelectronics, and inability to operate under constant temperature conditions. These shortcomings hinder their adaptability to a broad range of applications, especially when compared to thermal and optical sensors. To address these challenges, we introduce a proof-of-concept methodology that enables ferroelectric-based pyroelectric sensors to measure absolute temperatures with high accuracy and speed. Specifically, we demonstrate that a perturbation pulse (+0.8 V, duration = 180 ns) can serve as an effective probe for quantifying both absolute and dynamic temperatures across ferroelectric hafnium zirconium oxide (HZO) nanolaminates. The device demonstrates an ultrafast response time of ∼50 nanoseconds, offering one million readings per second and a temperature sensing accuracy comparable to the state-of-the-art temperature sensing accuracy of 1.0 K. The observed performance is attributed to the temperature-dependent change of transient negative differential capacitance and effective ferroelectric polarization of HZO. For potential applications, we successfully integrated the sensor with a commercially available universal serial bus interface, thereby demonstrating real-time temperature monitoring during data transfer and environmental heating activities. Our research significantly broadens the range of applications for pyroelectric sensors for both steady-state and rapid dynamic temperature measurements.

First-principles study of oxygen vacancies in LiNbO3-type ferroelectrics.

LiNbO3-type ferroelectric oxides, as an important class of non-centrosymmetric compounds, have received great attention due to their important and rich properties. Although oxygen vacancies are widely present, studies of them in LiNbO3-type ferroelectric oxides are rare. In this article, we consider three representative LiNbO3-type ferroelectric oxide materials LiNbO3, ZnTiO3 and ZnSnO3 to study the impact of oxygen vacancy doping using first principles calculations. LiNbO3 and ZnTiO3 have ferroelectrically active cations Nb5+ and Ti4+, while ZnSnO3 does not have ferroelectrically active cations. The distribution of the oxygen vacancy induced electrons are quite different in the three materials even though they have similar structures. In oxygen deficient LiNbO3-δ (δ = 0.083/f.u.), electrons are itinerant, while in ZnTiO3-δ and ZnSnO3-δ (δ = 0.083/f.u.) the electrons are localized. These results provide guidance for the application of oxygen vacancies in LiNbO3-type ferroelectric material devices.

Tuning optical absorption in perovskite (K,Na)NbO3 ferroelectrics.

The ability to tailor the electronic band structure and optical absorption by appropriate cationic substitution in perovskite oxide ferroelectrics is essential for many advanced electronic and optoelectronic applications of these materials. Here, we explored weak (Ba,Ni)-doping for reducing optical bandgaps in (K,Na)NbO3 ferroelectric films and ceramics. The optical absorption in the broad spectral range of (0.7-8.8) eV was investigated in polycrystalline doped, pure, and oxygen deficient films, in doped epitaxial films grown on different substrates, and in doped ceramics. By comparing optical properties of all films and ceramics, it was established that 1-2 at% of cationic substitutions or up to 10 at % of oxygen vacancies have no detectable effect on the direct (∼4.5 eV) and indirect (∼3.9 eV) gaps. Concurrently, substantial sub-gap absorption was revealed and ascribed to structural band tailing in epitaxial films and ceramics. It was suggested that owing to fundamental strain-property couplings in perovskite oxide ferroelectrics, inhomogeneities of lattice strain can lead to increased sub-gap absorption. The uncovered structurally induced sub-gap optical absorption can be relevant for other ferroelectric ceramics and thin films as well as for related perovskite oxides.