In ferroelectric materials, spontaneous symmetry breaking leads to a switchable electric polarization, which offers significant promise for nonvolatile memories. In particular, ferroelectric tunnel junctions (FTJs) have emerged as a new resistive switching memory which exploit polarization-dependent tunnel current across a thin ferroelectric barrier. Here we demonstrate FTJs with CMOS-compatible Zr-doped HfO$_2$ (Zr:HfO$_2$) ferroelectric barriers of just 1 nm thickness, grown by atomic layer deposition on silicon. These 1 nm Zr:HfO$_2$ tunnel junctions exhibit large polarization-driven electroresistance (19000$\%$), the largest value reported for HfO$_2$-based FTJs. In addition, due to just a 1 nm ferroelectric barrier, these junctions provide large tunnel current (> 1 A/cm$^2$) at low read voltage, orders of magnitude larger than reported thicker HfO$_2$-based FTJs. Therefore, our proof-of-principle demonstration provides an approach to simultaneously overcome three major drawbacks of prototypical FTJs: a Si-compatible ultrathin ferroelectric, large electroresistance, and large read current for high-speed operation.
Hafnia (HfO$_2$)-based thin films have promising applications in nanoscale electronic devices due to their robust ferroelectricity and integration with silicon. However, HfO$_2$ has various stable and metastable polymorphs with quite similar structures and energies. Identifying and stabilizing the ferroelectric functional phases of HfO$_2$ have attracted intensive research interest in recent years. In this work, first-principles calculations on (111)-oriented HfO$_2$ are used to discover that imposing an in-plane shear strain on the tetragonal phase induces a nonpolar to polar phase transition…
Atomic-scale understanding of HfO2 ferroelectricity is important to help address many challenges in developing reliable and high-performance ferroelectric HfO2 (fe-HfO2) based devices. Though investigated from different angles, a factor that is real device-relevant and clearly deserves more attention has largely been overlooked by previous research, namely, the fe-HfO2/dielectric interface. Here, we investigate the electronic structures of several typical interfaces formed between ultrathin fe-HfO2 and oxide dielectrics in the sub-3-nm region. We find that interface formation introduces strong…
Different dopants with their specific dopant concentration can be utilized to produce ferroelectric HfO$_2$ thin films. In this work it is explored for the example of Sr in a comprehensive first-principles study. Density functional calculations reveal structure, formation energy and total energy of the Sr related defects in HfO$_2$. We found the charge compensated defect including an associated oxygen vacancy Sr$_\text{Hf}$V$_\text{O}$ to strongly favour the non-ferroelectric, tetragonal P4$_\text{2}$/mnc phase energetically. In contrast, the uncompensated defect without oxygen vacancy Sr$_\te…
The ferroelectric properties of nanoscale silicon doped HfO$_2$ promise a multitude of applications ranging from ferroelectric memory to energy-related applications. The reason for the unexpected behavior has not been clearly proven and presumably include contributions from size effects and doping effects. Silicon incorporation in HfO$_2$ is investigated computationally by first-principles using different density functional theory (DFT) methods. Formation energies of interstitial and substitutional silicon in HfO$_2$ paired with and without an oxygen vacancy prove the substitutional defect as …
We report two series of structures representing two types of $180^\circ$ ferroelectric domain walls in $\mathrm{HfO_2}$ and $\mathrm{ZrO_2}$. We model the domain structures with different width by density functional theory calculations. The results reveal the dependency of domain wall energy and polarization on domain width. We show how the directions of polarization of ferroelectric domains can be determined from experimentally observed Hf atoms, despite the fact that the knowledge about the positions of O atoms is missing. The two series of structures thus provide more thorough interpretatio…
The discovery of ferroelectricity in HfO$_2$-based thin films opens up new opportunities for using this silicon-compatible ferroelectric to realize low-power logic circuits and high-density non-volatile memories. The functional performances of ferroelectrics are intimately related to their dynamic responses to external stimuli such as electric fields at finite temperatures. Molecular dynamics is an ideal technique for investigating dynamical processes on large length and time scales, though its applications to new materials is often hindered by the limited availability and accuracy of classica…
Hafnium oxide (HfO2)-based ferroelectrics offer remarkable promise for memory and logic devices in view of their compatibility with traditional silicon CMOS technology, high switchable polarization, good endurance and thickness scalability. These factors have led to steep rise in research on this class of materials over the past number of years. At the same time, only a few reports on the direct sensing of nanoscale ferroelectric properties exist, with many questions remaining regarding the emergence of ferroelectricity in these materials. While piezoresponse force microscopy (PFM) is ideally …
In this work we analyze the finite-size effects on the structural properties and on the polarization of the rhombohedral phase of HfO$_2$ subjected to a biaxial compressive strain. We show how the presence of surface charges affects the polarization, leading to a strong reduction with respect to its bulk value. This reduction can be ascribed to two mechanisms: the coupling between compressive strain and the phase-transition order parameter; the changes in the ferroelectric distortion. We give two alternative explanations of this phenomenon: from an atomistic point of view, analyzing the evolut…
Ferroelectric field-effect transistors (Fe-FETs) with ferroelectric hafnium oxide (FE HfO2) as gate insulator are being extensively explored as a promising device candidate for three-dimensional (3D) NAND memory application. FE HfO2 exhibits long retention over 10 years, high endurance over 1012 cycles, high speed with sub-ns polarization switching, and high remnant polarization of 10-30 μC/cm2. However, the performance of Fe-FETs is known to be much worse than FE HfO2 capacitors, which is not completely understood. In this work, we developed a comprehensive Fe-FET model based on a charge bala…
Spontaneous polarization is essential for ferroelectric functionality in non-centrosymmetric crystals. High-integration-density ferroelectric devices require the stabilization of ferroelectric polarization in small volumes. Here, atomic-resolution transmission electron microscopy imaging reveals that twinning-induced symmetry breaking in colloidal nanocrystals of centrosymmetric HfO2 leads to the formation of multiple polarization orders, which are associated with sub-nanometer ferroelectric and antiferroelectric phases. The minimum size limit of the ferroelectric phase is found to be ~4 nm3. …
The discovery of ferroelectric polarization in HfO2-based ultrathin films has spawned a lot of interest due to their potential applications in data storage. Recently, a new R3m rhombohedral phase was proposed to be responsible for the emergence of ferroelectricity in the [111]-oriented Hf0.5Zr0.5O2 thin films, but the fundamental mechanism of ferroelectric polarization in such films remains poorly understood. In this paper, we employ density-functional-theory calculations to investigate structural and polarization properties of the R3m HfO2 phase. We find that the film thickness and in-plane c…
It is generally accepted that oxygen vacancies play a central role in the emergence of ferroelectricity for HfO2-based materials, but the underlying mechanism still remains elusive. Herein, starting from the basic characterization circuit, we propose that the observed ferroelectricity is extrinsic. A key finding is that charged oxygen vacancies oscillate within the sample under repeated electric pulses, yielding a nonlinear current which behaves similarly to the polarization current for a normal ferroelectric. This unwanted current signal results in a ferroelectric-like hysteresis loop with bo…
The discovery of ferroelectricity in both pure and doped HfO$_2$-based thin films have revitalized the interest in using ferroelectrics for nanoscale device applications. To take advantage of this silicon-compatible ferroelectric, fundamental questions such as the origin of ferroelectricity and better approach to controlled realization of ferroelectricity at the nanoscale need to be addressed. The emergence of robust polarization in HfO$_2$-based thin films is considered as the cumulative effect of various extrinsic factors such as finite-size effects and surface/interface effects of small gra…
Recent observations of unusual ferroelectricity in thin films of HfO_2 and related materials have attracted broad interest to the materials and led to the emergence of a number of competing models for observed behaviors. Here we develop the electrochemical mechanism of observed ferroelectric-like behaviors, namely the collective phenomena of elastic and electric dipoles originated from oxygen vacancies formation in the vicinity of film surfaces, as well as from grain boundaries and other types of inhomogeneities inside the film. The ferroelectric phase is induced by the "electrochemical" coupl…
Though the electrical responses of the various polymorphs found in ferroelectric polycrystalline thin film HfO$_2$ are now well characterized, little is currently understood of this novel material's grain sub-structure. In particular, the formation of domain and phase boundaries requires investigation to better understand phase stabilization, switching, and interconversion. Here, we apply scanning transmission electron microscopy to investigate the atomic structure of boundaries in these materials. In particular, we find orthorhombic/orthorhombic domain walls and coherent orthorhombic/monoclin…
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 …
Atom Probe Tomography as an Emerging Tool for Understanding Defect-driven Mechanisms in HfO$_{2}$-based Ferroelectrics
Norwegian University of Science and Technology (NTNU)（挪威科技大学）；Helmholtz-Zentrum Berlin für Materialien und Energie（柏林亥姆霍兹材料能源中心）；Freie Universität Berlin（柏林自由大学）；University of Nebraska, Lincoln（内布拉斯加大学林肯分校）；University of Duisburg-Essen（杜伊斯堡-埃森大学）；Research Center Future Energy Materials and Systems（未来能源材料与系统研究中心）
Tunable Defect Engineering of Mo/TiON Electrode in Angstrom-Laminated HfO$_2$/ZrO$_2$ Ferroelectric Capacitors towards Long Endurance and High Temperature Retention
In this work, we demonstrate high performance indium-tin-oxide (ITO) transistors with the channel thickness down to 1 nm and ferroelectric Hf0.5Zr0.5O2 as gate dielectric. On-current of 0.243 A/mm is achieved on sub-micron gate-length ITO transistors with a channel thickness of 1 nm, while it increases to as high as 1.06 A/mm when the channel thickness increases to 2 nm. A raised source/drain structure with a thickness of 10 nm is employed, contributing to a low contact resistance of 0.15 Ωmm and a low contact resistivity of 1.1{\times}10-7 Ωcm2. The ITO transistor with a recessed channel and …
Ferroelectricity in hafnia is often regarded as a breakthrough discovery in ferroelectrics, potentially able to revolutionize the whole field. Despite increasing interests, a comprehensive understanding of the many factors driving the ferroelectric stabilization is still lacking. We here address the phase transition in terms of a Landau-theory-based approach, by analyzing symmetry-allowed distortions connecting the high-symmetry paraelectric tetragonal phase to the low-symmetry polar orthorhombic phase. By means of first-principles simulations, we find that the $Γ_{3-}$ polar mode is only weak…
We have investigated the field-induced-changes in both the magnetization and the polarization in ferromagnet/Insulator/ferroelectric (FM/I/FE) multilayer by following both the Stoner-Wohlfarth (SW) model and the Landau theory. It has been found that with the stresses introduced in the FM/I/FE structure by the fields, both the magnetization and the polarization states can be significantly modified and the combination of their states can be of multiple states. These results demonstrate the feasibility of combining both the spintronics and the ferroelectrics into the multiferroictronics.
Twist-induced Out-of-plane Ferroelectricity in Bilayer Hafnia
Institute of Materials Science and Engineering, Washington University in St. Louis（华盛顿大学圣路易斯分校材料科学与工程研究所）；Department of Mechanical Engineering and Material Science, Washington University in St. Louis（华盛顿大学圣路易斯分校机械工程和材料科学系）；Department of Physics and Astronomy, University of Nebraska, Lincoln（内布拉斯加大学林肯分校物理与天文学系）；Department of Physics, Washington University in St. Louis（华盛顿大学圣路易斯分校物理系）
We give detailed analysis of the effect of depolarizing field in nanometer-size ferroelectric capacitors studied by Kim et al. [Phys. Rev. Lett. 95, 237602 (2005)]. We calculate a critical thickness of the homogeneous state and its stability with respect to domain formation for strained thin films of BaTiO3 on SrRuO3/SrTiO3 substrate within the Landau theory. While the former (2.5nm) is the same as given by ab-initio calculations, the actual critical thickness is set by the domains at 1.6nm. There is a large Merz's activation field for polarization relaxation. Remarkably, the results show a_ne…
In this work, we carry out first-principles calculations and lattice mode analysis to investigate the polarization switching mechanism in HfO$_2$. Because the stability of the polar orthorhombic $Pca2_1$ phase of HfO$_2$ arises from a trilinear coupling, polarization switching requires the flipping of not only the polar $Γ_{15}^Z$ mode, but also at least one zone-boundary anti-polar mode. The coupling between the polar and anti-polar modes thus leads to substantial differences among different polarization switching paths. Specifically, our lattice-mode-coupling analysis shows that paths in whi…
In this work, we demonstrate scaled back-end-of-line (BEOL) compatible indium oxide (In2O3) transistors by atomic layer deposition (ALD) with channel thickness (Tch) of 1.0-1.5 nm, channel length (Lch) down to 40 nm, and equivalent oxide thickness (EOT) of 2.1 nm, with record high drain current of 2.0 A/mm at VDS of 0.7 V among all oxide semiconductors. Enhancement-mode In2O3 transistors with ID over 1.0 A/mm at VDS of 1 V are also achieved by controlling the channel thickness down to 1.0 nm at atomic layer scale. Such high current density in a relatively low mobility amorphous oxide semicondu…
The structural, thermal, and dielectric properties of the ferroelectric phase of HfO$_2$, ZrO$_2$ and Hf$_{0.5}$ Zr$_{0.5}$ O$_2$ (HZO) are investigated with carefully validated density functional computations. We find, that the free bulk energy of the ferroelectric orthorhombic Pca2$_{1}$ phase is unfavorable compared to the monoclinic P2$_{1}$/c and the orthorhombic Pbca phase for all investigated stoichiometries in the Hf$_χ$Zr$_{1-χ}$O$_2$ system. To explain the existence of the ferroelectric phase in nanoscale thin films we explore the Gibbs / Helmholtz free energies as a function of stre…
We report on a theoretical study on the tunneling anomalous Hall effect (TAHE) in a ferroelectric tunnel junction (FTJ), resulting from spin-orbit coupling (SOC) in the ferroelectric barrier. For ferroelectric barriers with large SOC, such as orthorhombic HfO2 and BiInO3, we predict values of the tunneling anomalous Hall conductivity (TAHC) measurable experimentally. We demonstrate strong anisotropy in TAHC depending on the type of SOC. For the SOC with equal Rashba and Dresselhaus parameters, we predict the perfect anisotropy with zero TAHC for certain magnetization orientations. The TAHC cha…
Because of its compatibility with semiconductor-based technologies, hafnia (HfO$_{2}$) is today's most promising ferroelectric material for applications in electronics. Yet, knowledge on the ferroic and electromechanical response properties of this all-important compound is still lacking. Interestingly, HfO$_2$ has recently been predicted to display a negative longitudinal piezoelectric effect, which sets it apart form classic ferroelectrics (e.g., perovskite oxides like PbTiO$_3$) and is reminiscent of the behavior of some organic compounds. The present work corroborates this behavior, by fir…
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…
