Ultrathin Ferroelectric Films Research Articles

Large resistive switching in ultrathin BiFeO3 thin films

Electrically induced resistive switching (RS) effects have been proposed as the basis for future non-volatile memories. In this work, 9 nm-thick BiFeO3 (BFO) epitaxial thin films were deposited on (001)-oriented SrTiO3 substrates by pulsed laser deposition and their resistive switching (RS) behaviors were investigated. A large resistive switching with ON/OFF ratio of ∼106 is observed, surpassing the performance of most resistive random access memories ever reported. The conducting filament is proposed to dominate the RS behavior in the positive voltage region, while the modulation of ferroelectric polarization is suggested to play a significant role in the negative voltage region. Our study significantly deepens the understanding of the physical origin of RS and could provide a reference for designing high-performance memories and memristors based on ultrathin ferroelectric films.

Ferroelectricity in Ultrathin Halide Perovskites.

Ferroelectricity has recently been demonstrated in germanium-based halide perovskites. We use first-principles-based simulations to study 4-18 nm CsGeBr3 films and develop a theory for ferroelectric ultrathin films. The theory introduces (i) a local order parameter, which identifies phase transitions into both monodomain and polydomain phases, and (ii) a dipole pattern classifier, which allows efficient and reliable identification of dipole patterns. Application of the theory to both halides CsGeBr3 and CsGeI3 and oxide BiFeO3 ultrathin ferroelectrics reveals two distinct scenarios. First, the films transition into a monodomain phase below the critical value of the residual depolarizing field. Above this critical value, the second scenario occurs, and the film undergoes a transition into a nanodomain phase. The two scenarios exhibit opposite responses of Curie temperature to thickness reduction. Application of a dipole pattern classifier reveals rich nanodomain phases in halide films: nanostripes, labyrinths, zig-zags, pillars, and lego domains.

Comparative performance of fluorite-structured materials for nanosupercapacitor applications

Over the last fifteen years, ferroelectric (FE) and antiferroelectric (AFE) ultra-thin films based on fluorite-structured materials have drawn significant attention for a wide variety of applications requiring high integration density. AFE ZrO2, in particular, holds significant promise for nanosupercapacitors, owing to its potential for high energy storage density (ESD) and high efficiency (η). This work assesses the potential of high-performance Hf1−xZrxO2 thin films encapsulated by TiN electrodes that show linear dielectric (LD), FE, and AFE behavior. A wake-up effect is observed for AFE ZrO2, a phenomenon barely reported for pure zirconium oxide and AFE materials in general, correlated with the disappearance of the pinched hysteresis loop commonly observed for Zr-doped HfO2 thin films. ESD and η are compared for FE, AFE, and LD samples at the same electrical field (3.5 MV/cm). As expected, ESD is higher for the FE sample (95 J/cm3), but η is ridiculously small (≈55%) because of the opening of the FE hysteresis curve, inducing high loss. Conversely, LD samples exhibit the highest efficiency (nearly 100%), at the expense of a lower ESD. AFE ZrO2 thin film strikes a balance between FE and LD behavior, showing reduced losses compared to the FE sample but an ESD as high as 52 J/cm3 at 3.5 MV/cm. This value can be further increased up to 84 J/cm3 at a higher electrical field (4.0 MV/cm), with an η of 75%, among the highest values reported for fluorite-structured materials, offering promising perspectives for future optimization.

Polar Bloch points in strained ferroelectric films

Topological domain structures have drawn great attention as they have potential applications in future electronic devices. As an important concept linking the quantum and classical magnetism, a magnetic Bloch point, predicted in 1960s but not observed directly so far, is a singular point around which magnetization vectors orient to nearly all directions. Here we show polar Bloch points in tensile-strained ultrathin ferroelectric PbTiO3 films, which are alternatively visualized by phase-field simulations and aberration-corrected scanning transmission electron microscopic imaging. The phase-field simulations indicate local steady-state negative capacitance around the Bloch points. The observation of polar Bloch points and their emergent properties consequently implies novel applications in future integrated circuits and low power electronic devices.

Artificial Domain Patterning in Ultrathin Ferroelectric Films via Modifying the Surface Electrostatic Boundary Conditions.

Nanoscale spatially controlled modulation of the properties of ferroelectrics via artificial domain pattering is crucial to their emerging optoelectronics applications. New patterning strategies to achieve high precision and efficiency and to link the resultant domain structures with device functionalities are being sought. Here, we present an epitaxial heterostructure of SrRuO3/PbTiO3/SrRuO3, wherein the domain configuration is delicately determined by the charge screening conditions in the SrRuO3 layer and the substrate strains. Chemical etching of the top SrRuO3 layer leads to a transition from in-plane a domains to out-of-plane c domains, accompanied by a giant (>105) modification in the second harmonic generation response. The modulation effect, coupled with the plasmonic resonance effect from SrRuO3, enables a highly flexible design of nonlinear optical devices, as demonstrated by a simulated split-ring resonator metasurface. This domain patterning strategy may be extended to more thin-film ferroelectric systems with domain stabilities amenable to electrostatic boundary conditions.

Surface Effect of Thickness-Dependent Polarization and Domain Evolution in BiFeO3 Epitaxial Ultrathin Films.

With the trend of device miniaturization, ultrathin ferroelectric films are gaining more and more attention. However, understanding ferroelectricity in this nanoscale context remains a formidable challenge, primarily due to the heightened relevance of surface effects, which often leads to the loss of net polarization. Here, the influence of surface effects on the polarization as a function of thickness in ultrathin BiFeO3 films is investigated using phase-field simulations. The findings reveal a notable increase in ferroelectric polarization with increasing thickness, with a particularly discernible change occurring below the 10 nm threshold. Upon accounting for surface effects, the polarization is marginally lower than the case without such considerations, with the disparity becoming more pronounced at smaller thicknesses. Moreover, the hysteresis loop and butterfly loop of the ultrathin film were simulated, demonstrating that the ferroelectric properties of films remain robust even down to a thickness of 5 nm. Our investigations provide valuable insights into the significance of ferroelectric thin films in device miniaturization.

Giant Electromechanical Effect in Piezoelectric Nanomembranes Based on Hf0.5Zr0.5O2.

Since ultrathin ferroelectric HfO2 films can be conformally grown by atomic layer deposition even on complex three-dimensional structures, new horizons in the development of next-generation piezoelectric devices are opened. However, hafnium oxide has a significant drawback for piezoelectric applications: its piezoelectric coefficients are much smaller than those of classical materials currently used in piezoelectric devices. Therefore, new approaches to the development of high-performance piezoelectric devices based on exploiting the unique properties of HfO2 are of paramount importance. In this work, a giant electromechanical effect in miniature piezoelectric membrane devices based on a 10 nm-thick ferroelectric Hf0.5Zr0.5O2 (HZO) film is experimentally demonstrated. Compared to the pure piezoelectric effect in the HZO film, the gain of the electromechanical response in membrane devices reaches 25 times. Numerical simulations confirm that this effect stems from the asymmetric shape of the membranes and can be further improved by designing the device geometry. Furthermore, according to first-principles calculations, an additional opportunity to improve the piezoelectric coefficient, and hence, the device efficiency is provided by the engineering of the mechanical stress in the HZO film. The proposed approach enables the development of new promising piezoelectric devices including miniature reflectors, nanoactuators, and nanoswitches.

Out-of-plane ferroelectricity and robust magnetoelectricity in quasi-two-dimensional materials.

Thin-film ferroelectrics have been pursued for capacitive and nonvolatile memory devices. They rely on polarizations that are oriented in an out-of-plane direction to facilitate integration and addressability with complementary metal-oxide semiconductor architectures. The internal depolarization field, however, formed by surface charges can suppress the out-of-plane polarization in ultrathin ferroelectric films that could otherwise exhibit lower coercive fields and operate with lower power. Here, we unveil stabilization of a polar longitudinal optical (LO) mode in the n = 2 Ruddlesden-Popper family that produces out-of-plane ferroelectricity, persists under open-circuit boundary conditions, and is distinct from hyperferroelectricity. Our first-principles calculations show the stabilization of the LO mode is ubiquitous in chalcogenides and halides and relies on anharmonic trilinear mode coupling. We further show that the out-of-plane ferroelectricity can be predicted with a crystallographic tolerance factor, and we use these insights to design a room-temperature multiferroic with strong magnetoelectric coupling suitable for magneto-electric spin-orbit transistors.

Studies on the nonlinear dielectric response in ferroelectric–dielectric composite system

The nonlinear dielectric response (NDR) of Bi3.25La0.75Ti3O12–Al2O3 systems has been studied. To reveal the effects of the dielectric layer (DL) systematically, a method based on the equivalent circuit analysis and parametric study is proposed. The consistency between the calculated results and the experimental results manifests the validity of the method. In addition to the Rayleigh coefficients varying monotonically with the capacitance of DL, it is revealed that the slope between the real and the imaginary parts of the complex capacitance under different ac voltages is related to the relative loss values of DL and the ferroelectric layer. The frequency dependence of the NDR parameters is also discussed. The method established in this work is useful for research on the devices based on the ferroelectric–dielectric system and the ultra-thin ferroelectric films.

Wake-Up Free Ultrathin Ferroelectric Hf0.5Zr0.5O2 Films.

The development of the new generation of non-volatile high-density ferroelectric memory requires the utilization of ultrathin ferroelectric films. The most promising candidates are polycrystalline-doped HfO2 films because of their perfect compatibility with silicon technology and excellent ferroelectric properties. However, the remanent polarization of HfO2 films is known to degrade when their thickness is reduced to a few nanometers. One of the reasons for this phenomenon is the wake-up effect, which is more pronounced in the thinner the film. For the ultrathin HfO2 films, it can be so long-lasting that degradation occurs even before the wake-up procedure is completed. In this work, an approach to suppress the wake-up in ultrathin Hf0.5Zr0.5O2 films is elucidated. By engineering internal built-in fields in an as-prepared structure, a stable ferroelectricity without a wake-up effect is induced in 4.5 nm thick Hf0.5Zr0.5O2 film. By analysis of the functional characteristics of ferroelectric structures with a different pattern of internal built-in fields and their comparison with the results of in situ piezoresponse force microscopy and synchrotron X-ray micro-diffraction, the important role of built-in fields in ferroelectricity of ultrathin Hf0.5Zr0.5O2 films as well as the origin of stable ferroelectric properties is revealed.

Ferroelectricity in Epitaxial Perovskite Oxide Bi2WO6 Films with One-Unit-Cell Thickness.

Retaining ferroelectricity in ultrathin films or nanostructures is crucial for miniaturizing ferroelectric devices, but it is a challenging task due to intrinsic depolarization and size effects. In this study, we have shown that it is possible to stably maintain in-plane polarization in an extremely thin, one-unit-cell thick epitaxial Bi2WO6 film. The use of a perfectly lattice-matched NdGaO3 (110) substrate for the Bi2WO6 film minimizes strain and enhances stability. We attribute the residual polarization in this ultrathin film to the crystal stability of the Bi-O octahedral framework against structural distortions. Our findings suggest that ferroelectricity can surpass the critical thickness limit through proper strain engineering, and the Bi2WO6/NdGaO3 (110) system presents a potential platform for designing low-energy consumption, nonvolatile ferroelectric memories.

Emergence of ferroelectricity in ZrO2 thin films on TiN/Si featuring high temperature sputtering method

ZrO2 has attracted attention as HfO2 and Hf1−xZrxO2 to nonvolatile memory applications because of its ferroelectric nature in orthorhombic phase, lower cost, and excellent thermal stability. Ferroelectricity in ZrO2 has been reported experimentally using several deposition methods. However, the fabrication of a ferroelectric ZrO2 thin film in the ultra-thin region of below 5 nm on TiN/Si remains a challenge. In this study, we examined the formation of ferroelectric ZrO2 ultrathin films on TiN/p+-Si using a high-temperature sputtering method while optimizing the involved substrates and processes.We clarified the importance of the underlying substrate selection to control the crystalline phase of ZrO2 thin films through comparing several types of substrates. TiN/p+-Si was found to be the most appropriate substrate for realizing ferroelectric ZrO2 films. Further, we demonstrated that plasma oxidation treatment improves the ferroelectricity and reduces the leakage current component of the 11-nm-thick ZrO2 films. Subsequently, we discussed the conditions for ferroelectricity by summarizing the switching polarization (PSW) of ZrO2 as functions of the ZrO2 thickness and sputtering temperature and realized the appearance of ferroelectricity in a 4 nm thick ZrO2 film with a PSW of 0.53 μC/cm2 and endurance properties until ∼108 cycles.

Improper ferroelectricity in ultrathin hexagonal ferrites films

Suppression of ferroelectricity in ultrathin films of improper ferroelectric hexagonal ferrites or manganites has been attributed to the effect of interfacial clamping; however, the quantitative understanding and related phenomenological model are still lacking. In this work, we report on the paraelectric-to-ferroelectric phase transition of epitaxial h-ScFeO3 films with different thicknesses through in situ reflection high-energy electron diffraction. Based on the interfacial clamping model and the Landau theory, we show that the thickness-dependence of the ferroelectric Curie temperature can be understood in terms of the characteristic length of an interfacial clamping layer and the bulk Curie temperature. Furthermore, we found that the critical thickness of improper ferroelectricity is proportional to the characteristic length of the interfacial clamping layer. These results reveal the essential role of mechanical clamping from interface on the improper ferroelectricity of hexagonal ferrites or manganites and could serve as the guidance to achieve robust improper ferroelectricity in ultrathin films.

Ferroelectricity in layered bismuth oxide down to 1 nanometer.

Atomic-scale ferroelectrics are of great interest for high-density electronics, particularly field-effect transistors, low-power logic, and nonvolatile memories. We devised a film with a layered structure of bismuth oxide that can stabilize the ferroelectric state down to 1 nanometer through samarium bondage. This film can be grown on a variety of substrates with a cost-effective chemical solution deposition. We observed a standard ferroelectric hysteresis loop down to a thickness of ~1 nanometer. The thin films with thicknesses that range from 1 to 4.56 nanometers possess a relatively large remanent polarization from 17 to 50 microcoulombs per square centimeter. We verified the structure with first-principles calculations, which also pointed to the material being a lone pair-driven ferroelectric material. The structure design of the ultrathin ferroelectric films has great potential for the manufacturing of atomic-scale electronic devices.

Understanding the Effect of Top Electrode on Ferroelectricity in Atomic Layer Deposited Hf0.5Zr0.5O2 Thin Films

It is commonly believed that the impact of the top electrodes on the ferroelectricity of hafnium-based thin films is due to strain engineering. However, several anomalies have occurred that put existing theories in doubt. This work carries out a detailed study of this issue using both theoretical and experimental approaches. The 10 nm Hf0.5Zr0.5O2 (HZO) films are prepared by atomic layer deposition, and three different top capping electrodes (W/MO/ITO) are deposited by physical vapor deposition. The electrical testing finds that the strain does not completely control the ferroelectricity of the devices. The results of further piezoelectric force microscopy characterization exclude the potential interference of the top capping electrodes and interface for electrical testing. In addition, through atomic force microscopy characterization and statistical analysis, a strong correlation between the grain size of the top electrode and the grain size of the HZO film has been found, suggesting that the grain size of the top electrode can induce the formation of the grain size in HZO thin films. Finally, the first-principles calculation is carried out to understand the impact of the strain and grain size on the ferroelectric properties of HZO films. The results show that the strain is the dominant factor for ferroelectricity when the grain size is large (>10 nm). However, when the grain size becomes thinner (<10 nm), the regulation effect of grain sizes increases significantly, which could bring a series of benefits for device scaling, such as device-to-device variations, film uniformity, and domain switch consistency. This work not only completes the understanding of ferroelectricity through top electrode modulation but also provides strong support for the precise regulation of ferroelectricity of nanoscale devices and ultrathin HZO ferroelectric films.

Physical origin of the endurance improvement for HfO2-ZrO2 superlattice ferroelectric film

HfO2-ZrO2 superlattice (SL) ferroelectric (FE) ultrathin films exhibit significant improvement in endurance performance compared with solid-solution HfxZr1−xO2 (HZO). Despite the experimental evidence, the underlying microscopic mechanisms of the enhanced reliability of SL remain elusive. This Letter explores the mechanism by performing first-principle calculations on SL and HZO systems. The enhanced endurance in the SL can be well explained by higher oxygen vacancy (Vo) migration energy barriers along the FE polarization direction, which slow down the increase in Vo. The suppression of Vo increase will potentially help maintain the stability of the FE phase and alleviate the fatigue. Based on this mechanism, we suggest that doping materials with higher Vo migration barriers can further improve the endurance of HfO2-based FE devices. This work facilitates the future development of HfO2-based FE devices with enhanced endurance and reliability.

Meron–antimeron annihilation induced by the electric field in a polar meron lattice

Polar topological domain structures may have potential applications in future memory devices. Exploring their dynamical behaviors is paramount to the device design. Here, the meron–antimeron annihilation processes induced by the electric field in ultrathin ferroelectric PbTiO3 films were studied by phase-field simulations. Two types of annihilation behaviors were identified: The merons with central polarizations parallel to the electric field will directly annihilate with their nearby antimerons; those antiparallel to the electric field will first be switched and then annihilate with antimerons. The annihilation ratio of meron–antimeron pairs (MAPs) decreases with the increase in the meron–antimeron distance. During annihilation processes, the positions of antimerons seldom change and the merons approach to antimerons at some critical electric fields. The annihilation probability of a meron is found to be closely related to its topological charge. Specifically, the restoration of an MAP from a partially annihilated state was observed under the decrease in the electric field. These results may have some indications to the development of polar-meron-based memory devices.

Changeable electroresistance in Pt/Pb(Zr,Ti)O3/(La,Sr)MnO3 tunnel junctions and memristive properties for synaptic plasticity emulation

Ferroelectric tunnel junctions (FTJs) are promising candidates for the next-generation memory technologies. The electroresistance mechanism, however, has been reported not only from the polarization-modulation of barrier profiles. Electrical migration of charged defects has also been observed as a possible origin for the resistive switching. Here, we achieve two kinds of electroresistance behaviors in Pt/Pb(Zr,Ti)O3/(La,Sr)MnO3 tunnel junctions by introducing oxygen vacancies in the Pb(Zr,Ti)O3 barrier. The oxygen vacancies are observed by x-ray photoelectron spectroscopy, and their effects on the widely adopted piezoresponse force microscopy characterizations of ultrathin ferroelectric films have been analyzed by AC voltage-dependent hysteresis loops. For the Pt/Pb(Zr,Ti)O3/(La,Sr)MnO3 device that is modulated by the polarization reversal, a counterclockwise resistance–voltage (R–V) relationship is observed due to the tunneling between high and low barriers, whereas the R–V hysteresis loop is changed to clockwise with the existence of oxygen vacancies, in which conductive filaments are formed in the Pb(Zr,Ti)O3 barrier. However, such an ionic electroresistance is not stable during repetitive switching. Further investigation on memristive behaviors is, thus, performed on the ferroelectric-controlled Pt/Pb(Zr,Ti)O3/(La,Sr)MnO3 tunnel junctions. An excellent linearity is achieved in continuous resistance change owing to the nucleation-limited-switching mode of domain switching in the Pb(Zr,Ti)O3 barrier, giving rise to spike-timing-dependent plasticity behaviors for the Hebbian rule of learning and memory. These results provide insight into the distinguishing of ferroelectric and ionic contributions in electroresistance of FTJ devices, facilitating deep understanding of nonvolatile resistive memories.

Alternating Current Field Effects in Atomically Ferroelectric Ultrathin Films.

In this work, atomically K1−xNaxNbO3 thin films are taken as examples to investigate the reversible and irreversible effects in a horizon plane, i.e., the changes of domain structures, phase states, free energies, etc., under a z-axis alternating current field via a phase-field method. The simulation results show the driving forces during the charging and discharging process, where there is a variation for the angles of the domain walls from 180° to 90° (and then an increase to 135°), which are the external electric field and domain wall evolution, respectively. As for the phase states, there is a transformation between the orthorhombic and rhombohedral phases which can’t be explained by the traditional polarization switching theory. This work provides a reasonable understanding of the alternating current field effect, which is essential in information and energy storage.

Thickness-Dependent Polar Domain Evolution in Strained, Ultrathin PbTiO3 Films.

Ferroelectric ultrathin films have great potential in electronic devices and device miniaturization with the innovation of technology. In the process of product commercialization, understanding the domain evolution and topological properties of ferroelectrics is a prerequisite for high-density storage devices. In this work, a series of ultrathin PbTiO3 (PTO) films with varying thicknesses were deposited on cubic KTaO3 substrates by pulsed laser deposition and were researched by Cs-corrected scanning transmission electron microscopy (STEM), reciprocal space mapping (RSM), and piezoresponse force microscopy (PFM). RSM experiments indicate the existence of a/c domains and show that the lattice constant varies continuously, which is further confirmed by atomic-scale STEM imaging. Diffraction contrast analysis clarifies that with the decrease in PTO film thickness, the critical thickness for the formation of a/c domains could be missing. When the thickness of PTO films is less than 6 nm, the domain configurations in the ultrathin PTO films are the coexistence of a/c domains and bowl-like topological structures, where the latter ones were identified as convergent and divergent types of meron. In addition, abundant 90° charged domain walls in these ultrathin PTO films were identified. PFM studies reveal clear ferroelectric properties for these ultrathin PTO films. These results may shed light on further understanding the domain evolution and topological properties in ultrathin ferroelectric PTO films.