Ferroelectric Hf0 Research Articles

Compact Physical Implementation of Spiking Neural Network Using Ambipolar WSe2 n-Type/p-Type Ferroelectric Field-Effect Transistor.

Spiking neural networks (SNNs) are attracting increasing interests for their ability to emulate biological processes, offering energy-efficient computation and event-driven processing. Currently, no devices are known to combine both neuronal and synaptic functions. This study presents an experimental demonstration of an ambipolar WSe2 n-type/p-type ferroelectric field-effect transistor (n/p-FeFET) integrated with ferroelectric Hf0.5Zr0.5O2 (HZO) to achieve both volatile and nonvolatile properties in a single device. The nonvolatile n-FeFET, driven by the stable ferroelectric properties of HZO, exhibits highly linear synaptic behavior. In contrast, the volatile p-FeFET, influenced by electron self-compensation in the ambipolar WSe2, enables self-resetting leaky-integrate-and-fire neurons. Integrating neuronal and synaptic functions in the same device allows for compact neuromorphic computing applications. Additionally, simulations of SNNs using experimentally calibrated synaptic and neuronal models achieved a 93.8% accuracy in MNIST digit recognition. This innovative approach advances the development of SNNs with high biomimetic fidelity and reduced hardware costs.

Hf0.4Zr0.6O2 Thickness-Dependent Transfer Characteristics of InxZn1-xOy Channel Ferroelectric FETs.

We investigate how the threshold voltage (VT) is adjusted to create a memory window (MW) in ferroelectric field-effect transistors (FeFETs) composed of ferroelectric Hf0.4Zr0.6O2 and InZnO (In2O3:ZnO = 9:1 wt %). Temperature-dependent polarization measurements reveal a dipole switching in Hf0.4Zr0.6O2. The properties of the n-type InZnO channel are examined by fabricating an oxide transistor with an HfO2 gate dielectric. Upon replacement of HfO2 with Hf0.4Zr0.6O2 in the oxide transistor, a counterclockwise MW is observed. Specifically, as the Hf0.4Zr0.6O2 thickness increases from 16 to 24 nm, the VT of the FeFET after a + gate voltage (VG) sweep remains nearly constant, while the VT after a -VG sweep shifts significantly from -0.9 to 0.5 V. The enlarged MW of approximately 2 V, which is proportional to the Hf0.4Zr0.6O2 thickness in the FeFET, can be explained by considering the balance between VG controllability across the gate stack and the ferroelectric switching of Hf0.4Zr0.6O2.

Ferroelectricity of Hf0.5Zr0.5O2 thin films grown by atomic layer deposition on epitaxial TiN bottom electrodes

In this study, the effects of the epitaxial TiN bottom electrode on the crystallinity and ferroelectricity of Hf0.5Zr0.5O2 (HZO) thin films were investigated. HZO thin films were deposited using atomic layer deposition on epitaxial TiN(100) on MgO(100), epitaxial TiN(111) on Al2O3(0001), and polycrystalline TiN on Si(100) for comparison. The HZO thin films on epitaxial TiN(100) exhibited the largest remanent polarization of ∼26 μC/cm2, with the largest orthorhombic phase fraction. Conversely, the HZO thin film on polycrystalline TiN showed the smallest remanent polarization ∼19 μC/cm2, with the smallest orthorhombic phase fraction. High-resolution transmission electron microscopy analysis confirmed the dominance of the orthorhombic phase in the HZO thin film on epitaxial TiN(100). Reliability tests showed that the HZO thin films on epitaxial TiN (100) exhibited superior retention with a smaller wake-up effect compared to those of the HZO thin films on polycrystalline TiN but they displayed inferior cycling endurance characteristics.

Characterizing polarization switching kinetics of ferroelectric Hf0.5Zr0.5O2 at cryogenic temperature

We have characterized polarization switching kinetics of Hf0.5Zr0.5O2 (HZO) at cryogenic temperature (T) down to 100 K. By the nucleation-limited-switching model with Lorentzian distribution fittings, the dependences of the average switching time (log τ1) and switching time distribution (ω) on T are extracted. As T decreases from 300 to 100 K, log τ1 first rapidly decreases and then gradually stabilizes. Meanwhile, ω exhibits different trends under different external electric fields (Eext), decreasing under low Eext while increasing under high Eext, eventually stabilizing at non-zero constants. With the further decrease in T (<100 K), log τ1 and ω exhibited by HZO are almost unchanged, indicating the intrinsic properties of ferroelectric multiple domains, which are different from the prediction in previous literature studies that log τ1 and ω will linearly decrease as T decreases.

Reconfigurable dielectric engineered WSe2/HZO mem-transistor

Abstract Hybrid systems coupling 2D semiconductors with functional ferroelectrics are attracting increasing attention due to their excellent electronic/optoelectronic properties and new functionalities through the multiple heterointerface interaction. In our device architecture, interfacial states are introduced on the ferroelectric Hf0.5Zr0.5O2 thin film as gate dielectric layer for charge trapping effect. Utilizing the collaborative effects of charge trapping and ferroelectric polarization behavior, a multifunctional 2D WSe2/HZO memtransistor is demonstrated with ultra-low off-state (dark) current of 10-13 A, high on/off ratio of 106 and linear conductance update. This device exhibits reliable memory properties and tunable synaptic functions including short-term plasticity (STP)/ long-term plasticity (LTP), paired pulse facilitation (PPF), spike-timing dependent plasticity (STDP), synaptic potentiation/depression, and filtering in a single device. Extensive endurance tests ensure robust stability (1000 switching cycles, 2000 s holding time) and the synaptic weight update in the device exhibits excellent linearity. Based on the experimental data, our devices eventually achieve an accuracy of 94.8% in artificial neural network simulations. These results highlight a new approach for constructing hybrid systems coupling 2D semiconductors with functional ferroelectrics in a single device for tuning synaptic weight, optimizing circuit design, and building artificial neuromorphic computing systems.

Mechanisms for enhanced ferroelectric properties in ultra-thin Hf0.5Zr0.5O2 film under low-temperature, long-term annealing

To gain insight into the ferroelectric mechanisms under reduced thermal budget and thickness scaling, a 4.6 nm ultra-thin ferroelectric Hf0.5Zr0.5O2 capacitor compatible with back-end-of-line (BEOL) processes (all conducted at temperatures ≤350 °C) is investigated in this work. Through O3 pretreatment at the bottom electrode (BE) interface and controlled temperature modulation of the crystalline phase, the capacitor exhibits exceptional ferroelectric (FE) properties following low-temperature (350 °C) and long-term (300 s) rapid thermal annealing (RTA). These properties include high remanent polarization (2Pr ∼ 28.53 μC/cm2), low coercive voltage (Vc ∼ 0.43 V), effective leakage suppression, robust endurance (∼1010 cycles without hard breakdown), and a desirable high dielectric constant. The main mechanisms identified include tetragonal phase nucleation under enhanced tensile stress via the oxidized BE layer (TiO2), crystalline growth controlled through RTA temperature modulation, and phase transition to the ferroelectric orthorhombic phase under electric field cycling. This research provides valuable insights for the development of BEOL-compatible nonvolatile FE memories.

Role of charge injection/de-trapping in imprint behavior of ferroelectric Hf0.5Zr0.5O2 thin film

Ferroelectric HfO2-based thin films have attracted increasing interest due to their potential applications in nonvolatile memory areas. However, their unique properties, such as imprint, lead to serious reliability issues. In this study, the origin of imprint behavior is investigated by using TiN/Hf0.5Zr0.5O2 (10 nm)/TiN MFM capacitors. By modulating the internal electric field during imprint, we discover that charge injection/de-trapping in metal–ferroelectric interfaces plays an essential role in imprint behavior rather than charge movement inside the FE layer. The asymmetric shift of the coercive field is also discussed, which is attributed to nonlinear interaction between polarization's bound charges and the electrode's screening charges. This suggests that controlling interface quality should effectively suppress imprint in HfO2-based thin films.

Three types of resistive switching in ferroelectric Hf0.5Zr0.5O2 films mediated by polarization reversal and oxygen vacancy migration

Three types of resistive switching in ferroelectric Hf0.5Zr0.5O2 films mediated by polarization reversal and oxygen vacancy migration

In situ grazing incidence synchrotron x-ray diffraction studies on the wakeup effect in ferroelectric Hf0.5Zr0.5O2 thin films

The discovery of ferroelectricity in HfO2 ultrathin films has gathered considerable interest from the microelectronic industry owing to their compatibility with complementary metal oxide semiconductor technology. However, a significant challenge in utilizing HfO2 thin films for commercial devices is the wakeup effect, which is an increase in polarization with the number of electric field cycles in HfO2-based capacitors. Despite efforts to develop wakeup-free HfO2 thin films, the root cause of this effect remains elusive. Some studies attribute it to the tetragonal (T) to orthorhombic (O) phase transformation, while others suggest it is due to the redistribution of oxygen vacancies within the HfO2 layer during electric field cycling. This study investigated the phase transformation dynamics and oxygen vacancy distributions in TiN/Hf0.5Zr0.5O2/TiN capacitors subjected to electric field cycling using in situ grazing incidence synchrotron x-ray diffraction and ex situ x-ray photoelectron spectroscopy. The as-grown HZO films were crystallized in a mixed phase consisting of monoclinic (M), tetragonal, and orthorhombic fractions. The T-phase volume fraction decreased continuously up to 10k electric field cycles. In contrast, the O-phase fraction increased within the first 100 cycles and then stabilized with further cycling. The redistribution of oxygen vacancies occurred continuously throughout the cycling process. The results revealed that continuous oxygen vacancy redistribution during electric field cycling resulted in phase transformation between the T-, O-, and M-phases. The study provides insight into the phase transformation dynamics and oxygen vacancy redistribution in TiN/Hf0.5Zr0.5O2/TiN capacitors during electric field cycling, shedding light on the underlying mechanisms of the wakeup effect.

Magnetically-induced enhancement of photocatalytic dye decomposition in ferroelectric Hf0.5Zr0.5O2 films

The film photocatalyst is easily recycled and has attracted the widely research interesting. Here the ferroelectric Hf0.5Zr0·5O2(HZO) thin film synthesized through the atomic layer deposition (ALD) method is used as a photocatalyst for the rhodamine B (RhB) dye decomposition under visible light irradiation. The photocatalytic RhB dye decomposition performances with or without an external magnetic field excitation provided by a commercial NdFeB magnet are experimentally characterized. With the increasing of the external direct-current (DC) magnetic field from 0 to 3000 Gs, the photocatalytic RhB dye decomposition ratio by HZO film obviously increases from 87.20 % to 98.17 %, which is attributed to the enhanced separation of the photo-induced positive and negative carrier due to the magnetic Lorentz effect. The magnetically-induced enhancement of photocatalysis in the ferroelectric HZO film, provides a method with these advantages of simple external excitation method, remarkable promotion effect and friendly-environment to enhance the dye decomposition ratio, and is potential in the practical application of photocatalytic dye wastewater treatment through harvesting the clean solar energy in future.

Theory of strain phase equilibria and diagrams

Chemical phase equilibria and phase diagrams are well established and have served as indispensable guides for designing materials through chemical tuning. However, a general thermodynamic theory for strain phase equilibria remains elusive despite extensive studies which have revealed dramatic impacts of mechanical strain on the stability of phases and domain states in solid-state materials. Here, we establish the thermodynamic theory of strain equilibria and a general framework for efficiently constructing multidomain and multiphase diagrams of arbitrarily strained solids under incoherent conditions. As examples, we obtain temperature-strain phase diagrams of ferroelectric PbTiO3, strongly correlated VO2, and unconventional ferroelectric Hf0.5Zr0.5O2. We reveal the analogs of the Gibbs phase rules, multiple- and multi-critical points, common-tangent construction, and level rule in strain equilibria to those in the familiar chemical phase equilibria. Our strain equilibria theory offers a powerful framework for predicting the thermodynamic stability of structural phases and domains in strained solids and for guiding the strain engineering of their functional properties.

Nonvolatile optical phase shift in ferroelectric hafnium zirconium oxide

A nonvolatile optical phase shifter is a critical component for enabling the fabrication of programmable photonic integrated circuits on a Si photonics platform, facilitating communication, computing, and sensing. Although ferroelectric materials such as BaTiO3 offer nonvolatile optical phase shift capabilities, their compatibility with complementary metal-oxide-semiconductor fabs is limited. Hf0.5Zr0.5O2 is an emerging ferroelectric material, which exhibits complementary metal-oxide-semiconductor compatibility. Although extensively studied for ferroelectric transistors and memories, its application to photonics remains relatively unexplored. Here, we show the optical phase shift induced by ferroelectric Hf0.5Zr0.5O2. We observed a negative change in refractive index at a 1.55 μm wavelength in a pristine device regardless of the direction of the applied electric field. The nonvolatile phase shift was only observed once in a pristine device. This non-reversible phase shift can be attributed to the spontaneous polarization within the Hf0.5Zr0.5O2 film along the external electric field.

The Investigation of Reduced Variation Effect in FinFETs With Ultrathin 3-nm Ferroelectric Hf₀.₅Zr₀.₅O₂

The Investigation of Reduced Variation Effect in FinFETs With Ultrathin 3-nm Ferroelectric Hf₀.₅Zr₀.₅O₂

Enlargement of Memory Window of Si Channel FeFET by Inserting Al₂O₃ Interlayer on Ferroelectric Hf₀.₅Zr₀.₅O₂

Enlargement of Memory Window of Si Channel FeFET by Inserting Al₂O₃ Interlayer on Ferroelectric Hf₀.₅Zr₀.₅O₂

Enhanced remnant polarization in ferroelectric Hf0.5Zr0.5O2 thin film capacitors through Mo top electrode by post-metallization annealing treatment

Zr-doped HfO2 (Hf0.5Zr0.5O2) ferroelectric thin films have garnered considerable attention due to their appealing attributes, including a large bandgap (>5 eV), low crystallization temperature, and compatibility with CMOS technology. In this study, we present the achievement of a substantial remnant polarization in ferroelectric Hf0.5Zr0.5O2 thin films, fabricated through atomic layer deposition, with Mo and TiN serving as the top and bottom electrodes, respectively. The Mo/Hf0.5Zr0.5O2/TiN capacitor exhibited commendable ferroelectric behavior and demonstrated high endurance within a thermal budget ranging from 400 to 500 °C. Leveraging the relatively low thermal expansion coefficient of the Mo top electrode facilitated the induction of in-plane tensile strain, fostering an increased formation of the ferroelectric orthorhombic phase within the Hf0.5Zr0.5O2 layer. Elevating the post-metallization annealing temperature to 500 °C yielded a substantial increase in 2Pr (≈54 μC/cm2) with excellent endurance exceeding 106 cycles. The influence of annealing temperature on the morphological and structural properties of Hf0.5Zr0.5O2 thin films was comprehensively analyzed through atomic force microscopy and grazing incidence X-ray diffraction analysis.

Performance improvements in complementary metal oxide semiconductor devices and circuits based on fin field-effect transistors using 3-nm ferroelectric Hf0.5Zr0.5O2

In this work, a conventional HfO2 gate dielectric layer is replaced with a 3-nm ferroelectric (Fe) HZO layer in the gate stacks of advanced fin field-effect transistors (FinFETs). Fe-induced characteristics, e.g., negative drain induced barrier lowering (N-DIBL) and negative differential resistance (NDR), are clearly observed for both p- and n-type HZO-based FinFETs. These characteristics are attributed to the enhanced ferroelectricity of the 3-nm hafnium zirconium oxide (HZO) film, caused by Al doping from the TiAlC capping layer. This mechanism is verified for capacitors with structures similar to the FinFETs. Owing to the enhanced ferroelectricity and N-DIBL phenomenon, the drain current (IDS) of the HZO-FinFETs is greater than that of HfO2-FinFETs and obtained at a lower operating voltage. Accordingly, circuits based on HZO-FinFET achieve higher performance than those based on HfO2-FinFET at a low voltage drain (VDD), which indicates the application feasibility of the HZO-FinFETs in the ultra-low power integrated circuits.Graphical abstract

Analysis of ferroelectric properties of ALD-Hf0.5Zr0.5O2 thin films according to oxygen sources

Ferroelectric Hf0.5Zr0.5O2 (HZO) thin films are mostly deposited with a thickness of less than 10 nm by an atomic layer deposition (ALD) process. Since the oxygen source used in the ALD process affects the residues in the deposited HZO films, the choice of oxygen source can be one of the important factors to improve ferroelectricity. From this point of view, the ferroelectric properties of 10-nm-thick ALD-HZO films according to the oxygen source (O3, H2O, and D2O) were comprehensively analyzed in this study. Heavy water (deuterium water, D2O) was used as a tracer to pinpoint the origin of hydrogen that could be derived from unreacted metal precursors or unreacted hydroxyl groups. As a result, it was revealed that the decrease in ferroelectric polarization and increase in leakage current observed in the H2O- and D2O-based HZO capacitors compared to the O3-based HZO capacitor were due to the oxygen source. These results highlight the importance of using O3 as a hydrogen-free oxygen source in the ALD process to achieve better ferroelectricity.

Anomalous polarization-switching phenomena and noteworthy pyroelectricity in ferroelectric Hf0.5Zr0.5O2 polycrystalline films

Hafnia-based oxide thin films exhibit unconventional robust ferroelectricity at the nanoscale, paving the way for advancements in next-generation nanoelectronics. However, the stability and dynamics of ferroelectric polarization in hafnia-based oxides films, particularly at the nanoscale, warrant further exploration. In this study, we delve into the factors influencing the formation of the ferroelectric phase. Our findings illuminate that the confinement effect of the capped layer enhances the stabilization of the metastable orthorhombic phase, thereby bolstering its ferroelectricity and endurance. Furthermore, we identify an unprecedented polarization-switching behavior in HfO2-based ferroelectric films, characterized by a decrease in the remanent polarization and an increase in the coercive field as the temperature drops. This peculiar phenomenon can be ascribed to the reduction in the long-range interaction of polarization dipoles upon cooling, as evidenced by the dielectric spectrum. The diminished long-range interaction results in the emergence of nanodomains and a re-entrant relaxer behavior, offering novel insights into the origin of ferroelectricity and the stability of ferroelectric polarization in hafnia-based thin films. Given the commendable compatibility of Hf0.5Zr0.5O2 films with Si substrates and a pyroelectric coefficient of −62.1 μC/m2·K, they emerge as a prime candidate for sensor device applications.

Ambipolar MoS2 Field Effect Transistors with Negative Photoconductivity and High Responsivity Using an Ultrathin Epitaxial Ferroelectric Gate

AbstractFerroelectric field effect transistors (FeFETs), characterized by their low power consumption and polarization effect, can be employed in photodetectors based on 2D materials. In this paper, a MoS2 phototransistor with epitaxial ferroelectric (Hf0.5Zr0.5)O2 (HZO) is reported as a gate dielectric layer. Gate‐dielectric‐polarization‐dependent ambipolar behavior is observed in the FET, and relatively low power consumption and hysteresis‐free loop are achieved in the FeFET. The anomalous negative photoconductivity (NPC) is observed as well. Possible reasons for such phenomenon are clarified including the photogating effect originating from the interface traps and the polarization‐dependent electric‐field control through ferroelectric gating. The high responsivity of −8.44 × 103 A W−1 in the negative photoconductivity as well as the response time of 500 ms are reported. The demonstrated Molybdenum disulfide (MoS2) FeFET photodetectors show great potential in the on‐chip complementary metal‐oxide semiconductor (CMOS)‐compatible circuits for multifunctional devices.

Persistent spin texture in ferroelectric Hf0.5Zr0.5O2

Persistent spin texture (PST) refers to the unidirectional spin configuration in momentum space and preserves the SU(2) spin rotation symmetry, which protects the spin coherence against the relaxation and renders an ultimately infinite spin lifetime. In this regard, it would be desirable to find high-quality quantum materials sustaining the intrinsic PST. Here, based on density-functional theory calculations, we show that the ferroelectric Hf0.5Zr0.5O2 sustains a PST over large area of Brillouin zone around the conduction band minimum, while the Rashba-type spin texture dominates around the valence band maximum. Based on the group-theoretical analysis, we construct an effective k·p Hamiltonian model and demonstrate that the PST arises from the significant anisotropy of spin splitting, which pins the spin–orbit field to certain direction. In addition, we elucidate the spin SU(2) symmetry for the discovered PST. Given the fact that Hf0.5Zr0.5O2 is compatible with silicon semiconductor technologies, our work discovers a high-quality oxide material sustaining the PST, which holds great promise for spin-orbitronic applications.