A newly developed fast molecular-dynamics method is applied to BaTiO3 ferroelectric thin-film capacitors with short-circuited electrodes or under applied voltage. The molecular-dynamics simulations based on a first-principles effective Hamiltonian clarify that dead layers (or passive layers) between ferroelectrics and electrodes markedly affect the properties of capacitors, and predict that the system is unable to hop between a uniformly polarized ferroelectric structure and a striped ferroelectric domain structure at low temperatures. Simulations of hysteresis loops of thin-film capacitors are also performed, and their dependence on film thickness, epitaxial constraints, and electrodes are discussed.
Time-dependent polarization relaxation behaviors induced by a depolarization field $E_{d}$ were investigated on high-quality ultrathin SrRuO$_{3}$/BaTiO$_{3}$/SrRuO$_{3}$ capacitors. The $E_d$ values were determined experimentally from an applied external field to stop the net polarization relaxation. These values agree with those from the electrostatic calculations, demonstrating that a large $E_{d}$ inside the ultrathin ferroelectric layer could cause severe polarization relaxation. For numerous ferroelectric devices of capacitor configuration, this effect will set a stricter size limit than…
We investigate the fatigue and refreshment by dc-electrical field of the electrical properties of Pt/Pb(Ti,Zr)O$_3$/Pt ferroelectric capacitors. We find an asymmetry in the refreshment, that is, the fatigued state can be refreshed by application of negative high dc-voltage to the top electrode, but no refreshment is measured by positive dc-voltage application. We also find that the fatigue can be prevented by driving the capacitor asymmetrically.
Structural studies on ultrathin SrRuO3/BaTiO3/SrRuO3 capacitors, with BaTiO3 thicknesses of between 5 nm and 30 nm, show well-defined interfaces between ferroelectric BaTiO3 and electrode SrRuO3 layers. In these capacitors, we cannot observe any extrinsic electrical effects due to either the formation of an insulating interfacial passive layer or passive-layer-induced charge injection. Such high quality interfaces result in very good fatigue endurance, even for the 5 nm thick BaTiO3 capacitor.
The epitaxial growth of multifunctional oxides on semiconductors has opened a pathway to introduce new functionalities to semiconductor device technologies. In particular, ferroelectric materials integrated on semiconductors could lead to low-power field-effect devices that can be used for logic and memory. Essential to realizing such field-effect devices is the development of ferroelectric metal-oxide-semiconductor (MOS) capacitors, in which the polarization of a ferroelectric gate is coupled to the surface potential of a semiconducting channel. Here we demonstrate that ferroelectric MOS capa…
We present a model for the leakage current in ferroelectric thin- film capacitors which explains two of the observed phenomena that have escaped satisfactory explanation, i.e. the occurrence of either a plateau or negative differential resistivity at low voltages, and the observation of a Positive Temperature Coefficient of Resistivity (PTCR) effect in certain samples in the high-voltage regime. The leakage current is modelled by considering a diffusion-limited current process, which in the high-voltage regime recovers the diffusion-limited Schottky relationship of Simmons already shown to be …
The influence of depolarizing field on the magnitude and stability of a uniform polarization in ferroelectric capacitors and tunnel junctions is studied using a nonlinear thermodynamic theory. It is predicted that, in heterostructures involving strained epitaxial films and metal electrodes, the homogeneous polarization state may remain stable against transformations into the paraelectric phase and into polydomain states down to the nanoscale. This result supports the possibility of depolarizing-field-related resistive switching in ferroelectric tunnel junctions with dissimilar electrodes. The …
The instability of ferroelectric ordering in ultra-thin films is one of the most important fundamental issues pertaining realization of a number of electronic devices with enhanced functionality, such as ferroelectric and multiferroic tunnel junctions or ferroelectric field effect transistors. In this paper, we investigate the polarization state of archetypal ultrathin (several nanometres) ferroelectric heterostructures: epitaxial single-crystalline BaTiO$_3$ films sandwiched between the most habitual perovskite electrodes, SrRuO$_3$, on top of the most used perovskite substrate, SrTiO$_3$. We…
First-principles modeling of ferroelectric capacitors presents several technical challenges, due to the coexistence of metallic electrodes, long-range electrostatic forces and short-range interface chemistry. Here we show how these aspects can be efficiently and accurately rationalized by using a finite-field density-functional theory formalism in which the fundamental electrical variable is the displacement field D. By performing calculations on model Pt/BaTiO3/Pt and Au/BaZrO3/Au capacitors we demonstrate how the interface-specific and bulk-specific properties can be identified and rigorousl…
In this study, we propose a measurement technique for evaluating ferroelectric polarization characteristics in ferroelectric field-effect transistors (FeFETs). Different from standard metal/ferroelectric/metal capacitors, the depletion and inversion phenomena in semiconductor substrates have to be carefully taken into account when evaluating the ferroelectric properties using fast voltage sweep as input. The non-equilibrium deep depletion is found to be the limiting factor for the accurate evaluation of ferroelectric properties in metal/ferroelectric/semiconductor capacitors. By connecting the…
We report on extensive domain wall motion in ferroelectric nanocapacitor arrays investigated by piezoresponse force microscopy. Under a much longer or higher bias voltage pulse, compared to typical switching pulse conditions, domain walls start to propagate into the neighbouring capacitors initiating a significant cross-talk. The propagation paths and the propagated area into the neighbouring capacitors were always the same under repeated runs. The experimental and the simulated results show that the observed cross-talk is related to the capacitor parameters combined with local defects. The re…
We report the dielectric properties of improper ferroelectric h-ErMnO$_3$. From the bulk characterisation we observe a temperature and frequency range with two distinct relaxation-like features, leading to high and even 'colossal' values for the dielectric permittivity. One feature trivially originates from the formation of a Schottky barrier at the electrode-sample interface, whereas the second one relates to an internal barrier layer capacitance (BLC). The calculated volume fraction of the internal BLC (of 8 %) is in good agreement with the observed volume fraction of insulating domain walls…
Going down to the limit of ultrathin films holds promise for a new generation of devices such as ferroelectric tunnel junctions or resistive memories. However, these length scales also make the devices sensitive to parasitic effects related to miniaturization, and a better understanding of what happens as size is reduced is of practical importance for the future development of these devices. As the experimental advances in materials preparation and characterization have come together with great progress in theoretical modeling of ferroelectrics, both theorists and experimentalists can finally …
We show experimental switching data on microscale capacitors of lead-zirconate-titanate (PZT), which reveal time-resolved domain behavior during switching on a 100-ns scale. For small circular capacitors, an unswitched domain remains in the center while complete switching is observed in square capacitors. The observed effect is attributed to the formation of vortex domain during polarization switching in circular capacitors. This dynamical behavior is modeled using the Landau-Liftshitz-Gilbert equations and found to be in detailed agreement with experiment. This simulation implies rotational m…
Results of the experimental study of the electromagnetic pumping of frequency 0.3 THz upon the soft mode phonons in the (Ba, Sr)TiO3 film are presented. Some features of the phonon state are revealed using the capacitor thermometer and the thermocouple. The soft mode phonon overheating estimated comparing changes of the planar capacitor capacitance was observed to be quite significant
Investigating the Electromechanical Behavior of Unconventionally Ferroelectric $Hf_{0.5}Zr_{0.5}O_{2}$-based Capacitors Through Operando Nanobeam X-ray Diffraction
Half of the energy is always lost when charging a capacitor. Even in the limit of vanishing resistance, half of the charging energy is still lost--to radiation instead of heat. While this fraction can technically be reduced by charging adiabatically, it otherwise places a fundamental limit on the charging efficiency of a capacitor. Here we show that this 1/2 limit can be broken by coupling a ferroelectric to the capacitor dielectric. Maxwell's equations are solved for the coupled system to analyze energy flow from the perspective of Poynting's theorem and show that (1) total energy dissipation…
The van der Waals layered material CuInP2S6 features interesting functional behavior, including the existence of four uniaxial polarization states, polarization reversal against the electric field through Cu ion migration, a negative-capacitance regime, and reversible extraction of Cu ions. At the heart of these characteristics lies the high mobility of Cu ions, which also determines the spontaneous polarization. Therefore, Cu migration across the lattice results in unusual ferroelectric behavior. Here, we demonstrate how the interplay of polar and ionic properties provides a path to ionically…
Epitaxial ferroelectric Hf0.5Zr0.5O2 films have been successfully integrated in a capacitor heterostructure on Si(001). The orthorhombic Hf0.5Zr0.5O2 phase, [111] out-of-plane oriented, is stabilized in the films. The films present high remnant polarization Pr close to 20 μC/cm2, rivaling with equivalent epitaxial films on single crystalline oxide substrates. Retention time is longer than 10 years for writing field of around 5 MV/cm, and the capacitors show endurance up to 1E9 cycles for writing voltage of around 4 MV/cm. It is found that the formation of the orthorhombic ferroelectric phase d…
The Boltzmann distribution of electrons poses a fundamental barrier to lowering energy dissipation in conventional electronics, often termed as Boltzmann Tyranny. Negative capacitance in ferroelectric materials, which stems from the stored energy of phase transition, could provide a solution, but a direct measurement of negative capacitance has so far been elusive. Here we report the observation of negative capacitance in a thin, epitaxial ferroelectric film. When a voltage pulse is applied, the voltage across the ferroelectric capacitor is found to be decreasing with time-in exactly the oppos…
In a recent Letter [N.A. Pertsev and H. Kohlstedt, Phys. Rev. Lett. 98, 257603 (2007)] the authors claim that "even nanoscale capacitors and tunnel junctions may have out of plane polarization sufficient for memory applications." Here we show in an elementary way that this conclusion is not substantiated by their calculations and that they should have come to the opposite conclusion within their approximations.
Access Rate-Dependent Endurance Behavior of Ferroelectric Hafnium Zirconium Oxide Capacitors
NaMLab gGmbH（NaMLab有限公司）；Queen’s University Belfast（贝尔法斯特女王大学）；Technical University Dresden（德累斯顿工业大学）；Intel Foundry（英特尔代工）；University Applied Sciences, Department of Applied Sciences and Mechatronics（应用科学大学应用科学与机电工程系）
An Unsupervised Machine Learning-based Framework for Wafer Scale Variability Analysis and Performance Prediction of Ferroelectric Hf0.5Zr0.5O2 Thin Film Capacitors
We investigate the nonlinear response of the domain wall velocity ($v$) to an external electric field ($E_{ext}$) in ferroelectric Si-doped HfO$_{2}$ thin film capacitors using piezoresponse force microscopy (PFM) and switching current measurements. We verified the reliability of the PFM images of ferroelectric domain switching by comparing the switched volume fraction in the PFM images with the time-dependent normalized switched polarization from the switching current data. Using consecutive time-dependent PFM images, we measured the velocity of the pure lateral domain wall motion at various …
We applied soft X-ray absorption spectroscopy to study the Ti L-edge in ferroelectric capacitors using a modified total electron yield method. The inner photo currents and the X-ray absorption spectra were polarization state dependent. The results are explained on the basis of photo electric effects and the inner potential in the ferroelectric capacitors as a result of back-to-back Schottky barriers superimposed by the potential due to the depolarization field. In general, the presented method offers the opportunity to investigate the electronic structure of buried metal-insulator and metal-se…
We report the discovery of serendipitous electrocaloric effects in commercial multilayer capacitors based on ferroelectric BaTiO3. Direct thermometry records ~0.5 K changes due to 300 kV cm-1, over a wide range of temperatures near and above room temperature. Similar results are obtained indirectly, via thermodynamic analysis of ferroelectric hysteresis loops. We compare and contrast these two results. Optimised electrocaloric multilayer capacitors could find applications in future cooling technologies.
Unconventional ferroelectricity, robust at reduced nanoscale sizes, exhibited by hafnia-based thin-films presents tremendous opportunities in nanoelectronics. However, the exact nature of polarization switching remains controversial. Here, we investigate epitaxial Hf0.5Zr0.5O2 (HZO) capacitors, interfaced with oxygen conducting metals (La0.67Sr0.33MnO3, LSMO) as electrodes, using atomic resolution electron microscopy while in situ electrical biasing. By direct oxygen imaging, we observe reversible oxygen vacancy migration from the bottom to the top electrode through HZO and reveal associated r…
Electrical energy storage systems (EESSs) with high energy density and power density are essential for the effective miniaturization of future electronic devices. Among different EESSs available in the market, dielectric capacitors relying on swift electronic and ionic polarization-based mechanisms to store and deliver energy already demonstrate high power densities. However, different intrinsic and extrinsic contributions to energy dissipations prevent ceramic-based dielectric capacitors from reaching high recoverable energy density levels. Interestingly, relaxor ferroelectric-based dielectri…
In this paper, impedance spectroscopy study was performed to establish the electrical property and microstructure relations of the as-deposited and post-annealed polycrystalline CCTO films prepared on Pt/Ti/SiO2/Si (100) substrates by pulsed-laser deposition (PLD). Our results demonstrated that the as-deposited polycrystalline CCTO film was made of insulating grain boundaries with semiconducting grains, indicating that the high-dielectric-constant is attributed to the barrier layer capacitor (BLC) effects. The simple resistor-capacitor (RC) equivalent circuit and the modified constant phase el…
Enhancing the performance of nanoscale ferroelectric (FE) field-effect transistors and FE capacitors for memory devices and logic relies on miniaturizing the metal electrode/ferroelectric area and reducing the thickness of the insulator. Although size reductions improve data retention, deliver lower voltage threshold switching, and increase areal density, they also degrade the functional electric polarization. There is a critical, nanometer length $t_\mathrm{FE}^*$ below which the polarization disappears owing to depolarizing field effects. Here we show how to overcome the critical thickness l…
Epitaxial growth of Ba0.6Sr0.4Ti1-xZrxO3 (0/leqx\leq0.3) composition spread thin film library on SrRuO3/SrTiO3 layer by combinatorial pulsed laser deposition (PLD) is reported. X-ray diffraction and energy dispersive x-ray spectroscopy studies showed an accurate control of the film phase and composition by combinatorial PLD. A complex evolution of the microstructure and morphology with composition of the library is described, resulting from the interplay between epitaxial stress, increased chemical pressure and reduced elastic energy upon Zr doping. Statistical and temperature-related capaciti…
Zirconia and hafnia based thin films have attracted tremendous attention in the last decade due to their unexpected ferroelectric behavior at the nanoscale, which facilitates the downscaling of ferroelectric devices. The present work reports a novel ferroelectric rhombohedral phase of ZrO2 that can be achieved in thin films grown on (111)- Nb:SrTiO3 substrates by ion-beam sputtering. Structural and ferroelectric characterizations reveal that the (111)-oriented ZrO2 films are under epitaxial compressive strain and display a switchable ferroelectric polarization of about 20.2 μC/cm2 with a coerc…
About ten years after ferroelectricity was first reported in doped HfO2 polycrystalline films, there is tremendous interest in this material and ferroelectric oxides are once again in the spotlight of the memories industry. Great efforts are being made to understand and control ferroelectric properties. Epitaxial films, which have fewer defects and a more controlled microstructure than polycrystalline films, can be very useful for this purpose. Epitaxial films of ferroelectric HfO2 have been much less investigated, but after the first report in 2015 significant progress has been achieved. This…
We study the ferroelectric stability and surface structural properties of an oxygen-terminated hexagonal YMnO$_3$ ultra-thin film using density functional theory. Under an open circuit boundary condition, the ferroelectric state with the spontaneous polarization normal to the (0001) surface, is found to be metastable in a single domain state despite the presence of a depolarizing field. We establish a connection between the result and the role of improper ferroelectric transition. Our results imply that improper ferroelectric ultrathin films can have rather unique properties that are distincti…
Designing high endurance Hf0.5Zr0.5O2 capacitors through engineered recovery from fatigue for non-volatile ferroelectric memory and neuromorphic hardware
The consideration of size-induced ferroelectric-paraelectric phase transition for conventional and incipient ferroelectrics thin films with perovskite structure was carried out in phenomenological theory framework of Ginsburg-Landau-Devonshire. The more general form of surface free energy expansion that includes intrinsic surface stress tensor, surface piezoelectric effect and electrostriction as well as quadratic and quartic powers of surface polarization has been considered. The analytical expressions for thickness dependence of transition temperature was derived both for the conventional an…
This review covers the important advances in recent years in the physics of thin film ferroelectric oxides, the strongest emphasis being on those aspects particular to ferroelectrics in thin film form. We introduce the current state of development in the application of ferroelectric thin films for electronic devices and discuss the physics relevant for the performance and failure of these devices. Following this we cover the enormous progress that has been made in the first principles computational approach to understanding ferroelectrics. We then discuss in detail the important role that stra…
We report studies of ferroelectricity in ultra-thin perovskite films with realistic electrodes. The results reveal stable ferroelectric states in thin films less than 10 Åthick with polarization normal to the surface. Under short-circuit boundary conditions, the screening effect of realistic electrodes and the influence of real metal/oxide interfaces on thin film polarization are investigated. Our studies indicate that metallic screening from the electrodes is affected by the difference in work functions at oxide surfaces. We demonstrate this effect in ferroelectric PbTiO$_3$ and BaTiO$_3$ fil…
In thin film ferroelectric capacitor the chemical and electronic structure of the electrode/FE interface can play a crucial role in determining the kinetics of polarization switching. We investigate the electronic structure of a Pt/BaTiO3/SrTiO3:Nb capacitor using time-resolved photoemission spectroscopy. The chemical, electronic and depth sensitivity of core level photoemission is used to probe the transient response of different parts of the upper electrode/ferroelectric interface to voltage pulse induced polarization reversal. The linear response of the electronic structure agrees quantitat…
Interface effects on the ferroelectric behavior of PbTiO$_3$ ultrathin films deposited on SrTiO$_3$ substrate are investigated using an interatomic potential approach with parameters fitted to first-principles calculations. We find that the correlation of atomic displacements across the film/substrate interface is crucial for the stabilization of the ferroelectric state in films a few unit-cells thick. We show that the minimum film thickness for the appearance of a spontaneous polarized domain state is not an intrinsic property of the ferroelectric film but depends on the polarizability of the…
Ferroelectric films usually have phase states and physical properties very different from those of bulk ferroelectrics. Here we propose free-standing ferroelectric-elastic multilayers as a bridge between these two material systems. Using a nonlinear thermodynamic theory, we determine phase states of such multilayers as a function of temperature, misfit strain, and volume fraction fi of ferroelectric material. The numerical calculations performed for two classical ferroelectrics - PbTiO3 and BaTiO3 - demonstrate that polarization states of multilayers in the limiting cases fi -> 0 and fi -> 1 c…
The films of order-disorder type ferroelectrics were considered in the mean field approximation taking into account depolarization field. It was shown that size effects in this system could be described on the base of bulk system equation of state with Curie temperature dependent on the film thickness. The critical size hc and critical temperature Tc of phase transition from ferroelectric to paraelectric phase was calculated allowing for the depolarization field contribution. The comparison of the polarization dependence on the film thickness, temperature and electric field for the films of or…
The temperature-dependent polarization of SrTiO_3 thin films is investigated using confocal scanning optical microscopy. A homogeneous out-of-plane and inhomogeneous in-plane ferroelectric phase are identified from images of the linear electrooptic response. Both hysteretic and non-hysteretic behavior are observed under a dc bias field. Unlike classical transitions in bulk ferroelectrics, local ferroelectricity is observed at temperatures far above the dielectric permittivity maximum. The results demonstrate the utility of local probe experiments in understanding inhomogeneous ferroelectrics.
A reduction of polarization in ultra-thin ferroelectric films appears to be fundamental to ferroelectricity at the nanoscale. For the model system PbTiO3 on SrTiO3, we report observation of the polarization vs. thickness relation. Distinct periodicity changes of ferroelectric domains obtained from x-ray diffraction and total energy calculations reveal a linear lowering of the polarization below a critical thickness of ~12 nm. Independent polarization and tetragonality measurements provide insight into the fundamental relation between polarization and tetragonality in nanoscale ferroelectrics.
We review the role that first-principles calculations have played in understanding the effects of substrate-imposed misfit strain on epitaxially grown perovskite ferroelectric films. We do so by analyzing the case of BaTiO$_3$, complementing our previous publications on this subject with unpublished data to help explain in detail how these calculations are done. We also review similar studies in the literature for other perovskite ferroelectric-film materials.
Far-infrared and terahertz spectroscopy of ferroelectric soft and central modes in thin films on substrates is reviewed. In addition to classical displacive proper ferroelectrics, also incipient and relaxor ferroelectrics and multiferroics are discussed. Special attention is paid to differences between the soft-mode behavior in thin films and bulk materials (ceramics and single crystals) and their influence on the low-frequency permittivity. Particularly the effects of the thin film strains and depolarizing electric fields of the probing waves on the grain boundaries are emphasized. The soft-m…
We have modified Landau-Khalatnikov approach and shown that both the polar lattice and the screened charged defects determine the response of disordered ferroelectric-semiconductors. This system exhibits the spatially inhomogeneous switching under the external field while Landau-Khalatnikov model describes homogeneous switching with the sharp pyroelectric coefficient peak near the thermodynamic coercive field value. Our model gives more realistic pyroelectric hysteresis loop shape without any peaks near the coercive field and describes both qualitatively and quantitatively typical Pb(Zr,Ti)O_3…
The depolarization fields set up to due to uncompensated surface charges in a ferroelectric thin film can suppress the ferroelectric phase below a critical size. Recent experiments show that 180 degree domain structures can help to stabilize ferroelectricity in films as thin as 3 unit cells. We study the influence of domain structures on the size-dependent properties of ferroelectric thin films using time-dependent Ginzburg-Landau theory. The model incorporates the effect of depolarization field by considering non-ferroelectric passive layers at the top and bottom surfaces. We show that the 18…
The ground-state polarization of PbTiO3 thin films is studied using a microscopic effective Hamiltonian with parameters obtained from first-principles calculations. Under short-circuit electrical boundary conditions, (001) films with thickness as low as three unit cells are found to have a perpendicularly polarized ferroelectric ground state with significant enhancement of the polarization at the surface.
