Redistribution Of Vacancies Research Articles

Interplay between vacancy-induced hydrogen segregation and stress-induced vacancy redistribution causing embrittlement of alpha-iron

ABSTRACT This study proposes a novel mechanism of intergranular fracture in alpha-iron, focusing on the effects of trapped vacancies, H atoms, and their synergistic interplay under tensile strain. We present a methodology for the introduction of H into grain boundaries (GBs) resulting in a realistic distribution by considering H – H interactions. Accordingly, optimal H concentrations were determined under specific environmental conditions for GBs with and without vacancy-induced segregation under zero and 2% tensile strain, respectively. Subsequently, the reduction in cohesive energy at GBs was evaluated at the optimal H concentration under these conditions. In the case of H segregation without vacancies at zero applied strain, the reduction in the cohesive energy ranged approximately from 15% to 35% for all the GB configurations. Eventually, vacancy segregation increased H concentration at the GBs, defined as vacancy-induced H segregation. The vacancy-induced H segregation resulted in a 60%–117% increase in H concentration and a 70%–80% decrease in cohesive energy at a vacancy concentration of 7.491 / nm 2 under zero applied strain. The proposed vacancy-induced H-segregation mechanism explained the delayed fracture in steel. Furthermore, the effect of tensile strain on embrittlement was elucidated, with strain-induced vacancy redistribution and vacancy-induced H segregation synergistically promoting GB decohesion, resulting in a 73%–93% reduction in cohesive energy at the same vacancy concentration.

Resetting the Drift of Oxygen Vacancies in Ultrathin HZO Ferroelectric Memories by Electrical Pulse Engineering

Ferroelectric HfO2‐based films incorporated in nonvolatile memory devices offer a low‐energy, high‐speed alternative to conventional memory systems. Oxygen vacancies have been rigorously cited in literature to be pivotal in stabilizing the polar noncentrosymmetric phase responsible for ferroelectricity in HfO2‐based films. Thus, the ability to regulate and control oxygen vacancy migration in operando in such materials would potentially offer step changing new functionalities, tunable electrical properties, and enhanced device lifespan. Herein, a novel in‐ operando approach to control both wake‐up and fatigue device dynamics is reported. Via clever design of short ad hoc square electrical pulses, both wake‐up can be sped up and both fatigue and leakage inside the film can be reduced, key factors for enhancing the performance of memory devices. Using plasmon‐enhanced photoluminescence and dark‐field spectroscopy (sensitive to <1% vacancy variation), evidence that the electrical pulses give rise to oxygen vacancy redistribution is provided and it is shown that pulse engineering effectively delays wake‐up and reduces fatigue characteristics of the HfO2‐based films. Comprehensive analysis also includes impedance spectroscopy measurements, which exclude any influence of polarization reversal or domain wall movement in interpretation of results.

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.

Phase Transformation Driven by Oxygen Vacancy Redistribution as the Mechanism of Ferroelectric Hf0.5Zr0.5O2 Fatigue

AbstractAs a promising candidate for nonvolatile memory devices, the hafnia‐based ferroelectric system has recently been a hot research topic. Although significant progress has been made over the past decade, the endurance problem is still an obstacle to its final application. In perovskite‐based ferroelectrics, such as the well‐studied Pb[ZrxTi1−x]O3 (PZT) family, polarization fatigue has been discussed within the framework of the interaction of charged defects (such as oxygen vacancies) with the moving domains during the switching process, particularly at the electrode‐ferroelectric interface. Armed with this background, a hypothesis is set out to test that a similar mechanism can be in play with the hafnia‐based ferroelectrics. The conducting perovskite La‐Sr‐Mn‐O is used as the contact electrode to create La0.67Sr0.33MnO3 / Hf0.5Zr0.5O2 (HZO)/ La0.67Sr0.33MnO3 capacitor structures deposited on SrTiO3‐Si substrates. Nanoscale X‐ray diffraction is performed on single capacitors, and a structural phase transition from polar o‐phase toward non‐polar m‐phase is demonstrated during the bipolar switching process. The energy landscape of multiphase HZO has been calculated at varying oxygen vacancy concentrations. Based on both theoretical and experimental results, it is found that a polar to non‐polar phase transformation caused by oxygen vacancy redistribution during electric cycling is a likely explanation for fatigue in HZO.

A thermo-chemo-mechanically coupled peridynamics for investigating crack behavior in solids

In engineering applications, the phenomenon of cracking is often accompanied by a coupled multiphysics effect. Peridynamics (PD) is an effective approach for solving cracking problems, but currently, no general PD model accounts for the coupling of multiple physical fields. In this work, we develop a PD model of coupled deformation, heat conduction, species diffusion, and chemical reactions. First, we establish the equations for mass, linear momentum, and energy. Then we establish fully coupled constitutive laws that interpret the interactions between the various fields and formulate evolution equations that govern the flux of species and heat. These laws and equations are developed based on the inequality of energy dissipation and the principles of chemical kinetics. Species diffusion and chemical reactions are treated as separate processes to study their effects on the Helmholtz free energy density of solids and the subsequent formation and propagation of cracks. In addition, certain coupling coefficients are calibrated by equating the corresponding physical quantities in the PD model with those in continuum mechanics. Four specific cases are simulated to validate the model, including redistribution of vacancies in ceramics, hydrogen traps, and embrittlement in metals.

Oxygen vacancy redistribution and ferroelectric polarization relaxation on epitaxial perovskite films during an electrocatalytic process

Ferroelectric catalysis BaTiO3 films show negative ferroelectric polarization drives the oxygen vacancies redistribution to the surface accelerating the adsorption of reactants and charge transfer, resulting in an enhanced OER performance.

Significant Degradation Reduction in Metal Oxide Thin-Film Transistors via the Interaction of Ionized Oxygen Vacancy Redistribution, Self-Heating Effect, and Hot Carrier Effect

In this work, device degradation of metal oxide (MO) thin-film transistors (TFTs) under positive bias stress, linear stress, and saturation stress is systematically investigated. A significant degradation reduction in InGaZnO TFTs is observed for the first time under saturation stress. Incorporated with electric field simulations and temperature simulations, a degradation model, considering the interaction of ionized oxygen vacancy redistribution, self-heating effect, and hot carrier effect, is tentatively proposed to understand the degradation behaviors under various stress combinations. Moreover, a similar degradation reduction phenomenon is also reproduced in InSnZnO TFTs, demonstrating the applicability of the proposed degradation model in MO TFTs.

Tunable voltage polarity-dependent resistive switching characteristics by interface energy barrier modulation in ceria-based bilayer memristors for neuromorphic computing

Synaptic characteristics with tunable dependence on the voltage polarity are demonstrated in ceria (CeO2) and Gd-doped ceria (GDC) bilayer memristors with respect to their stacking orders. Both Pt/GDC/CeO2/Pt and Pt/CeO2/GDC/Pt memristors with different oxide stacking orders exhibit analog, linear, and symmetric synaptic weights for potentiation and depression, paired-pulse facilitation, and short- and long-term plasticity (STP and LTP, respectively). Potentiation and depression behaviors are highly linear and symmetric thanks to the stacking of more oxygen-deficient GDC layer with CeO2, which facilitates the redistribution of oxygen vacancies for analog resistance change. These memristors have opposite dependence of synaptic weight updates on the polarity of potentiation and depression voltages for the stacking order of CeO2 and GDC, which are consistently interpreted by voltage-driven energy barrier modulation at the interface between CeO2 and GDC or with Pt electrodes via oxygen vacancy redistribution. Recognition simulation with modified handwritten digits patterns using a two-layer perceptron neural network exhibits accuracy of approximately 88% with achieved dynamic range, linearity, symmetry, and precision states. These synaptic characteristics are also demonstrated in a 32 × 32 crossbar array of GDC-top memristors. This verifies the potential of bilayer memristors for application in artificial synapse networks in neuromorphic computing systems.

Conversion between Metavalent and Covalent Bond in Metastable Superlattices Composed of 2D and 3D Sublayers.

Reversible conversion over multimillion times in bond types between metavalent and covalent bonds becomes one of the most promising bases for universal memory. As the conversions have been found in metastable states, an extended category of crystal structures from stable states via redistribution of vacancies, research on kinetic behavior of the vacancies is highly in demand. However, it remains lacking due to difficulties with experimental analysis. Herein, the direct observation of the evolution of chemical states of vacancies clarifies the behavior by combining analysis on charge density distribution, electrical conductivity, and crystal structures. Site-switching of vacancies of Sb2Te3 gradually occurs with diverged energy barriers owing to their own activation code: the accumulation of vacancies triggers spontaneous gliding along atomic planes to relieve electrostatic repulsion. Studies on the behavior can be further applied to multiphase superlattices composed of Sb2Te3 (2D) and GeTe (3D) sublayers, which represent superior memory performances, but their operating mechanisms were still under debate due to their complexity. The site-switching is favorable (suppressed) when Te-Te bonds are formed as physisorption (chemisorption) over the interface between Sb2Te3 (2D) and GeTe (3D) sublayers driven by configurational entropic gain (electrostatic enthalpic loss). Depending on the type of interfaces between sublayers, phases of the superlattices are classified into metastable and stable states, where the conversion could only be achieved in the metastable state. From this comprehensive understanding on the operating mechanism via kinetic behaviors of vacancies and the metastability, further studies toward vacancy engineering are expected in versatile materials.

Unravelling the role of oxygen vacancies on the current transport mechanisms in all-perovskite nickelate/titanate heterojunctions for nonvolatile memory applications

The micrometer-sized nickelate–titanate heterojunctions with LaNiO3 (LNO) electrode have been fabricated to investigate the dominant current transport mechanisms under positive and negative bias. The LNO/SmNiO3 (SNO)/Nb:SrTiO3 (NSTO) heterojunction exhibits a highly rectifying feature with a very low leakage in a broad temperature region (from 200 to 425 K), which is attributed to the formation of a Schottky-like barrier at the SNO/NSTO interface. In addition, it is found that the trap defects (i.e., oxygen vacancies) play an essential role in determining the current density (J)–voltage (V) characteristics irrespective of the voltage polarity. The leakage current at low electric fields (<0.25 MV/cm) is dominated by temperature-enhanced trap assisted tunneling process, which is caused by the interface oxygen vacancy induced states. Further analysis suggests that, at high fields (>1.2 MV/cm), the leakage is ascribed to the bulk-limited field enhanced thermal ionization of trapped carriers in the SNO film (i.e., Poole–Frenkel emission). Specially, the oxygen vacancy redistribution near the SNO/NSTO heterointerface driven by a high temperature (425 K) or high electrical field (>3.8 MV/cm) stress is emphasized to account for the transition from the Schottky contact limited to bulk-limited conduction mechanism (i.e., space charge limited conduction). This work will benefit the further analysis of the resistive switching phenomena in nickelate-based devices, showing a potential for nonvolatile memory applications.

Electric field induced degradation of high-voltage PTCR ceramics

This study investigates the degradation of the PTCR material BaTiO3 in high DC voltage, as it is important for the application as heater in electric cars. Impedance spectroscopy was used to gain information on the degradation. The different individual contributions (Ri, Qi) are correlated to the respective features of the microstructure. Besides degradation in electric fields, field-free oxidation and reduction were conducted to examine the influence of oxygen vacancy concentration on the resistivity. The results show a higher resistivity after degradation in the electric field and after oxidation. In contrast, reducing the sample decreases the resistivity. The impedance analysis shows that mostly the grain boundary resistance is influenced during degradation. Likely, a local oxygen vacancy redistribution occurs at grain boundaries. This redistribution is caused by the locally very high electric fields, which in turn influence space charge and Schottky barriers, leading to a change in resistivity of the PTCR material.

Highly enhanced ferroelectricity in HfO2-based ferroelectric thin film by light ion bombardment.

Continuous advancement in nonvolatile and morphotropic beyond-Moore electronic devices requires integration of ferroelectric and semiconductor materials. The emergence of hafnium oxide (HfO2)-based ferroelectrics that are compatible with atomic-layer deposition has opened interesting and promising avenues of research. However, the origins of ferroelectricity and pathways to controlling it in HfO2 are still mysterious. We demonstrate that local helium (He) implantation can activate ferroelectricity in these materials. The possible competing mechanisms, including He ion-induced molar volume changes, vacancy redistribution, vacancy generation, and activation of vacancy mobility, are analyzed. These findings both reveal the origins of ferroelectricity in this system and open pathways for nanoengineered binary ferroelectrics.

Synthesis of Fe1-xS Nanoparticles with Various Superstructures by a Simple Thermal Decomposition Route and Their Magnetic Properties

Pyrrhotite nanoparticles with 5C and 3C superstructures were synthesized via a simple one-step thermal decomposition method in which hexadecylamine was used as a solvent at various reaction temperatures (TR). Structural analysis showed that at TR = 360 °C, almost uniform in size and shape Fe7S8 nanoparticles with 3C superstructure are formed, and an increase in the reaction temperature leads to the formation of Fe9S10 nanoparticles (5C superstructure), herewith a significant increase in the size of nanoparticles is observed. High-temperature magnetic measurements in 5 repeated heating-cooling cycles revealed that after the first heating branch in the Fe9S10 samples, the λ—Peak transition disappears, and the magnetization has a Weiss-type behavior characteristic of the Fe7S8 sample. The change in the behavior of magnetization can be explained by the redistribution of iron vacancies, which changes the initial phase composition of nanoparticles.

Oxygen Vacancy-Dependent Synaptic Dynamic Behavior of TiO x -Based Transparent Memristor

Transparent synaptic devices remain great prospects for a future comprehensive simulation of artificial synapses with the combination of photoelectric coupling characteristics in the neuromorphic system. In this article, one type of memristors based on a stack structure of ITO/TiO <sub xmlns:mml="http://www.w3.org/1998/Math/MathML" xmlns:xlink="http://www.w3.org/1999/xlink">y</sub> /TiO <sub xmlns:mml="http://www.w3.org/1998/Math/MathML" xmlns:xlink="http://www.w3.org/1999/xlink">x</sub> /TiN with high transmittance ( T > 81%) is fabricated, in which an oxygen-deficient TiO <sub xmlns:mml="http://www.w3.org/1998/Math/MathML" xmlns:xlink="http://www.w3.org/1999/xlink">y</sub> layer between TiO <sub xmlns:mml="http://www.w3.org/1998/Math/MathML" xmlns:xlink="http://www.w3.org/1999/xlink">x</sub> and ITO top electrode is introduced to adjust the gradual current characteristics during the SET/RESET process. Furthermore, the devices with different thickness ratios (1:4, 1:2, 1:1, 2:1) of oxygen-deficient TiO <sub xmlns:mml="http://www.w3.org/1998/Math/MathML" xmlns:xlink="http://www.w3.org/1999/xlink">y</sub> active layers are designed to realize the adjustability of the multilevel resistance state and the analog resistive switching (RS) behavior and improve electrical performances and synaptic simulation characteristics. Meantime, the device based on optimum thickness ratio (1:2) offers excellent uniformity for 1000 cycles and better nonlinearity (0.69) at a low programming power consumption, which reveals further simulation of essential synaptic functions, including paired-pulse facilitation (PPF), and spike-timing-dependent plasticity (STDP) as well as learning-relearning characteristics. In addition, oxygen concentration gradient could be regulated by controlling the thickness ratio to drive oxygen vacancy redistribution at the interfacial layer, which are also demonstrated by high-resolution transmission electron microscopy (HRTEM) and improve electronic properties and analog modulation characteristics.

High temperature ferroelectric domain wall memory

For automotive and space applications, the nonvolatile ferroelectric domain wall random access memory (DWRAM) is required to work at a wide temperature range of −40 °C to +150 °C. However, the wall current generally decays with the retention time at high temperatures with the uncertain mechanism. Here we observed the peaked domain wall (DW) currents to decay with time at 450 K in LiNbO3 single crystals, which was correlated with the charge injection into domain wall regions in the mobility of 6.4 × 10−9 cm2/V·s. The extrinsic charge injection suppresses the intrinsic diode-like DW current due to the local Li/O vacancy redistribution to compensate the domain boundary charge. But the injected charge can be removed at an opposite poling voltage and can be frozen upon cooling down to 300 K. The traces of frozen wall regions become conducting upon the wall erasure. Once the memory write and read times are far shorter than the charge injection time, the DWRAM shows good retention of written information with a large on/off current ratio of ~104 at 450 K, suitable to the applications in some extreme conditions.

Metal–insulator transition tuned by oxygen vacancy migration across TiO2/VO2 interface

Oxygen defects are essential building blocks for designing functional oxides with remarkable properties, ranging from electrical and ionic conductivity to magnetism and ferroelectricity. Oxygen defects, despite being spatially localized, can profoundly alter global properties such as the crystal symmetry and electronic structure, thereby enabling emergent phenomena. In this work, we achieved tunable metal–insulator transitions (MIT) in oxide heterostructures by inducing interfacial oxygen vacancy migration. We chose the non-stoichiometric VO2-δ as a model system due to its near room temperature MIT temperature. We found that depositing a TiO2 capping layer on an epitaxial VO2 thin film can effectively reduce the resistance of the insulating phase in VO2, yielding a significantly reduced ROFF/RON ratio. We systematically studied the TiO2/VO2 heterostructures by structural and transport measurements, X-ray photoelectron spectroscopy, and ab initio calculations and found that oxygen vacancy migration from TiO2 to VO2 is responsible for the suppression of the MIT. Our findings underscore the importance of the interfacial oxygen vacancy migration and redistribution in controlling the electronic structure and emergent functionality of the heterostructure, thereby providing a new approach to designing oxide heterostructures for novel ionotronics and neuromorphic-computing devices.

Dynamics of the spatial separation of electrons and mobile oxygen vacancies in oxide heterostructures

In the search for an oxide-based 2D electron system with a large concentration of highly mobile electrons, a promising strategy is to introduce electrons through donor doping while spatially separating electrons and donors to prevent scattering. In $\mathrm{SrTi}{\mathrm{O}}_{3}$, this can be achieved by tailoring the oxygen vacancy profile through reduction, e.g., by creating an interface with an oxygen scavenging layer. Through reduction, oxygen atoms are removed close to the interface, leaving behind oxygen vacancies in the $\mathrm{SrTi}{\mathrm{O}}_{3}$ lattice and mobile electrons in the $\mathrm{SrTi}{\mathrm{O}}_{3}$ conduction band. The commonly assumed picture is that the oxygen vacancies then remain confined close to the interface while the electrons leak a few nanometers into the bulk, resulting in an electron-defect separation and a highly mobile, oxide-based 2D electron system. So far it has remained unclear how the confinement and electron-defect separation develop over time. Here, we present transient finite element simulations that consider three driving forces acting on the oxygen vacancy distribution: diffusion due to the concentration gradient, drift due to the intrinsic electric field, and an oxygen vacancy trapping energy that holds oxygen vacancies at the interface. Our simulations show that at room temperature, three distinct regions are formed in $\mathrm{SrTi}{\mathrm{O}}_{3}$ within days: (1) Oxygen vacancies are partially held at the interface due to the oxygen vacancy trapping energy. (2) The accompanying positive space charge causes an oxygen vacancy depletion layer with large electron concentration and high mobility just below the interface. This electron-defect separation, indeed, leads to a highly conductive region. (3) While we are able to describe measured conductivity data with an oxygen vacancy trapping energy of $\ensuremath{-}0.2$ eV, this value does not prevent oxygen vacancy diffusion into the bulk: A diffusion front progresses into the bulk and leads to significant conductivity arising over the first micrometer within a couple of months. An enhanced oxygen vacancy trapping energy of $\ensuremath{-}0.5$ eV or below would suppress this loss of confinement, leading to a static and pronounced electron-defect separation. Consequently, our results highlight the importance of oxygen vacancy redistribution and suggest the trapping energy of oxygen vacancies at the interface as an important design parameter for oxygen-vacancy-based 2D electron systems.

Modulation of the resistive switching of BiFO3 thin films through electrical stressing

The resistive switching (RS) of Au/BiFeO3/SrRuO3 samples was shown to be controllable by using a thermal treatment and an electrical stressing method. Such a modulation of resistive switching effect can be associated to the oxygen vacancy movement and redistribution within the BiFeO3 thin film and the trapping/detrapping of charge carriers at the interfaces. After the application of a negative voltage to the thin film for a stressing period, a resistive switching reversal effect occurred and the current retention ability in the low resistance state increased, indicating an increase in the trap density at the interface and an enhancement of the charge carrier trapping ability. The trap density, trap level, and Schottky barrier height all display corresponding trends in their values as a result of the modulation of RS effect. The results indicate that the greater the accumulation of oxygen vacancies at any the film/electrode interface, when a reverse bias is applied the higher the resistance ratio was under reverse bias. Its diffusion process was likely to be hindered and the trapped charge carriers could be retained after a long time of electrical stressing.

Memory Switching and Threshold Switching in a 3D Nanoscaled NbOX System

The 3D crossbar arrays provide a cost-effective approach for high-density integration of resistive switching random-access memory (RRAM). A selector device or self-selective cells can be used to inhibit the sneaking current from the unselected cells. The coexistence of memory switching (MS) with inherent nonlinearity and threshold switching (TS) with high current density in an individual material system will lead to technological benefits for memory integration and neuromorphic computing. However, the reported conductive filament (CF)-type MS and TS combining devices cannot meet the requirements for practical applications, as these devices lack built-in nonlinearity in memory mode and display low current density and large relaxing time in the selector mode. In this letter, we report a 3D TiN/TiO2/NbOX/Pt device with MS and TS before and after the forming processes. In the MS mode, this device shows >50 nonlinearity, a 100 ON/OFF ratio, non-volatility, and stable homogeneous switching due to vacancy redistribution. In the TS mode, owing to the metal–insulator transition, a high ON-state current (1.6 MA/cm 2), high switching speed (<40 ns), and low relaxation time (<50 ns) are observed.

Spatial Redistribution of Interstitial Atoms and Vacancies in Semiconductors under the Influence of Pulsed Laser Irradiation

Spatial Redistribution of Interstitial Atoms and Vacancies in Semiconductors under the Influence of Pulsed Laser Irradiation