Electromigration Of Oxygen Vacancies Research Articles

Feld-induced modulation of two-dimensional electron gas at LaAlO3/SrTiO3 interface by polar distortion of LaAlO3

Since the discovery of two-dimensional electron gas at the LaAlO3/SrTiO3 interface, its intriguing physical properties have garnered significant interests for device applications. Yet, understanding its response to electrical stimuli remains incomplete. Our in-situ transmission electron microscopy analysis of a LaAlO3/SrTiO3 two-dimensional electron gas device under electrical bias reveals key insights. Inline electron holography visualized the field-induced modulation of two-dimensional electron gas at the interface, while electron energy loss spectroscopy showed negligible electromigration of oxygen vacancies. Instead, atom-resolved imaging indicated that electric fields trigger polar distortion in the LaAlO3 layer, affecting two-dimensional electron gas modulation. This study refutes the previously hypothesized role of oxygen vacancies, underscoring the lattice flexibility of LaAlO3 and its varied polar distortions under electric fields as central to two-dimensional electron gas dynamics. These findings open pathways for advanced oxide nanoelectronics, exploiting the interplay of polar and nonpolar distortions in LaAlO3.

Time-dependent electrical and electroluminescence properties of In-substituted CaSnO3 and CaSnO3:Pr thin films prepared by a chemical solution deposition method

CaSnO3, CaSn0.9In0.1O3−δ, and Ca0.995Pr0.005Sn0.9In0.1O3−δ thin films sandwiched between (In0.975Sn0.025)2O3−δ thin-film electrodes were prepared by a chemical solution deposition method. The electric and electroluminescence properties were investigated by applying dc (direct current) voltages to the films. No appreciable current was detected for the CaSnO3 thin film. When constant dc voltage was applied to the CaSn0.9In0.1O3−δ and the Ca0.995Pr0.005Sn0.9In0.1O3−δ thin films, current was close to zero just after applying the voltage, increased with increasing time at the beginning, reached a maximum at a certain time, and then decreased with increasing time. The current increased by annealing at 673 K in air and decreased reversibly by quenching from 1323 K. Ca0.995Pr0.005Sn0.9In0.1O3−δ thin film showed reddish white electroluminescence due to f-f transitions of Pr3+ ions. The time dependence of the luminance was similar to that of the current. The results were discussed in relation to oxygen absorption and desorption at high temperatures and electromigration of oxygen vacancies at room temperature.

Regulation of flux-closure domain structures via oxygen vacancies and charged scanning probe microscopy

Manipulation of topological structures has become one of the most interesting topics in ferroelectrics through multiple excitations due to their prospective applications in electro-mechanical-optic devices. Scanning probe microscopy (SPM) has been developed as a powerful tool to manipulate the polar state in ferroic materials, in which the electric field induced by charged SPM enables dynamic coupling between the switching of the polar states and electromigration of oxygen vacancies, resulting in unknown influences of oxygen vacancy on the polar state in ferroelectric topological structures. Here, we regulate the polar state by considering oxygen vacancies and a non-uniform electric field under the charged SPM experiment for flux-closure domain structures in PbTiO3 thin films. The charged SPM probe can excite the growth of newly flux-closure domains to improve the density of topological states. In contrast, oxygen vacancies are found to suddenly prohibit the evolution of the flux-closure domain structure, when their concentration jumps to a threshold value. Our results might give guidelines to increase and stabilize the memory unit through co-modulating the electric field and ions injection in the information field.

Impact of AC and DC Electric Fields on the Microstructure Evolution in Strontium Titanate

Herein, the impact of AC and DC electric fields on microstructure evolution in strontium titanate is investigated. The focus is on nonthermal effects by using current‐blocking electrodes. The seeded polycrystal technique allows investigating the impact of a DC electric field on grain growth for different grain‐boundary orientations and the impact of the surrounding atmosphere. As in previous studies, faster grain growth is observed at the negative electrode. This effect is stronger for the (100) orientation and in reducing atmosphere. In AC electric field at 1450 °C, a low‐enough frequency results in faster grain growth at both electrodes. These findings agree well with previous studies, where an electromigration of oxygen vacancies is found to cause a local reduction at the negative electrode, resulting in less space charge, less cationic segregation, and a higher grain‐boundary mobility. At 1500 °C, AC electric fields are found to cause a complete grain growth stagnation at very small grain sizes. This behavior is unexpected; the physical reasons are not clear. Herein, a brief study of sintering in DC electric field reveals slightly faster sintering if a field is applied.

Utilizing time domain electrical methods to monitor MLCCs' degradation

The continued development of BaTiO3-based multilayer ceramic capacitors has contributed to further miniaturization by reducing the thickness of each dielectric layer for different voltage range components. MLCC designs that achieve higher volumetric capacitive efficiency must be balanced with stable properties over long operational times at higher fields and temperatures, raising concerns about their reliability. To improve the reliability and slow transient mechanisms of oxygen vacancy electromigration that drive the degradation of insulation resistance of MLCCs, we need to develop new models and improved metrologies to enhance the performance of MLCCs. This paper demonstrates how electrical characterization techniques, such as thermally stimulated depolarization current and highly accelerated life test, can be used to better understand MLCCs' degradation and assess their reliability. Also, the limitations of existing lifetime prediction models and their shortcomings of using mean time to failure in predicting the lifetime of MLCCs are discussed along with future perspectives on evaluating the reliability of MLCCs.

Влияние ионов Li на мемристорные свойства конденсаторных структур на основе нанокомпозита (Co-=SUB=-40-=/SUB=-Fe-=SUB=-40-=/SUB=-B-=SUB=-20-=/SUB=-)-=SUB=-x-=/SUB=-(LiNbO-=SUB=-3-=/SUB=-)-=SUB=-100-x-=/SUB=-

The paper reveals the influence of Li, B and the composition of metal contacts on the processes of resistive switching in memristive structures M/NC/D/M. After field exposure in structures Cu/(Co50Fe50)Х(LiNbO3)100-Х/s-LiNbO3/Cu/sitall, Cu/(Co50Fe50)Х(LiNbO3)100-Х/d-LiNbO3/Cu/sitall and Cu/(Co40Fe40B20)Х(SiO2)100-Х/d-LiNbO3/Cu/sitall at x < 13 at.% was detected a residual voltage (up to 16 mV) due to the electromigration of Li ions, that leading to a "reversible" type of VAC hysteresis and instability of the time dependencies of induced resistive states. In the structures of Cu/(Co40Fe40B20)Х(LiNbO3)100-Х/s-LiNbO3/Cu/sitall, Cr/Cu/Cr/(Co40Fe40B20)Х(LiNbO3)100-Х/s-LiNbO3/Cr/Cu/Cr/sitall containing B, the residual voltage is reduced by formation of chemical compounds B with percolated Li atoms. When limiting the electromigration of Li ions, the main mechanism of resistive switching is the processes of electromigration of oxygen vacancies in the dielectric oxide layer. Suppression of residual voltage in the Cr/Cu/Cr/(Co50Fe50)Х(LiNbO3)100-Х/s-LiNbO3/Cr/Cu/Cr/sitall structure due to the introduction of a Cr buffer layer that does not dissolve Li leads to the absence of bipolar resistive switching in these structures.

Epitaxial ferroelectric memristors integrated with silicon

Neuromorphic computing requires the development of solid-state units able to electrically mimic the behavior of biological neurons and synapses. This can be achieved by developing memristive systems based on ferroelectric oxides. In this work we fabricate and characterize high quality epitaxial BaTiO3-based memristors integrated with silicon. After proving the ferroelectric character of BaTiO3 we tested the memristive response of LaNiO3/BaTiO3/Pt microstructures and found a complex behavior which includes the co-existence of volatile and non-volatile effects, arising from the modulation of the BaTiO3/Pt Schottky interface by the direction of the polarization coupled to oxygen vacancy electromigration to/from the interface. This produces remanent resistance loops with tunable ON/OFF ratio and asymmetric resistance relaxations. These properties might be harnessed for the development of neuromorphic hardware compatible with existing silicon-based technology.

Controlling Memristance and Negative Differential Resistance in Point‐Contacted Metal–Oxides–Metal Heterojunctions: Role of Oxygen Vacancy Electromigration and Electron Hopping

Nonvolatile resistive switching memristance devices with a high on/off ratio are desirable for nanoelectronics such as resistive random‐access memory (RRAM) and in‐memory computing. Here, bipolar resistive switching in point‐contacted W/LaAlO3/SrTiO3(111) heterojunctions is reported, in which a Schottky barrier is formed at the metal/oxides interface, and 2d electron gas is formed at the interface of perovskite oxides. A negative differential resistance is observed in the RESET process. The result shows that the observed resistive switching is strongly associated with oxygen‐vacancies (OVs) in oxides with dominating contributions from electron hopping between OV trap sites, and can be controlled by oxygen annealing and electron injection. Remarkably, a method is developed by continuous RESET processes to increase the high resistance state by 1–3 orders of magnitude, with an on/off ratio enhanced from ≈10 to ≈104. The work provides a promising pathway to understand conduction mechanism of oxides memristors and promote its application in RRAM and in‐memory computing.

Key Role of Oxygen-Vacancy Electromigration in the Memristive Response of Ferroelectric Devices

Ferroelectric memristors are intensively studied due to their potential implementation in data storage and processing devices. In this work we show that the memristive behavior of metal/ferroelectric oxide/metal devices relies on the competition of two effects: the modulation of metal/ferroelectric interface barriers by the switchable ferroelectric polarization and the electromigration of oxygen vacancies, with the depolarizing field playing a fundamental role in the latter. We simulate our experimental results with a phenomenological model that includes both effects and we reproduce several non-trivial features of the electrical response, including resistance relaxations observed after external poling. Besides providing insight into the underlying physics of these complex devices, our work suggests that it is possible to combine non-volatile and volatile resistive changes in single ferroelectric memristors, an issue that could be useful for the development of neuromorphic devices.

Exchange of Ions across the TiN/TaOx Interface during Electroformation of TaOx-Based Resistive Switching Devices

Valence Change Model describes the resistive switching in metal oxides-based devices as due to electro-reduction of the oxide and subsequent electro-migration of oxygen vacancies. Here we present cross-sectional X-Ray Energy Dispersive Spectroscopy elemental maps of Ta, O, N, and Ti in electro-formed TiN/TaO2.0/TiN structures. O, N, and Ti were exchanged between anode and functional oxide in devices formed at high power (~1 mW) but the exchange was below the detection limit at low power (<0.5 mW). All structures exhibit similar Ta-enriched and O-depleted filament formed by the elemental segregation in the functional oxide by the temperature gradient. The elemental interchange is interpreted as due to Fick's diffusion caused by high temperatures in the gap of the filament and is not an essential part of electro-formation.

Strain-Inhibited Electromigration of Oxygen Vacancies in LaCoO3.

The oxygen vacancy profile in LaCoO3 exhibits rich phases with distinct structures, symmetries, and magnetic properties. Exploration of the lattice degree of freedom of LaCoO3 in the transition between these different structural phases may provide a route to enable new functionality in oxide materials with potential applications. To date, the oxygen vacancy profile transition in LaCoO3 has mainly been induced by transition-metal doping or thermal treatment. Epitaxial strain was proposed to compete with the lattice degree of freedom but has not yet been rationalized. Here, the experimental findings of strain-inhibited structural transition from perovskite to brownmillerite during the electromigration of oxygen vacancies in epitaxial LaCoO3 thin films are demonstrated. The results indicate that the oxygen vacancy ordering phase induced by the electric field is suppressed locally by both epitaxial strain field and external loads shown by in situ aberration-corrected (scanning)/ transmission electron microscopy. The demonstrated complex interplay between the electric and strain fields in the structural transitions of LaCoO3 opens up prospects for manipulating new physical properties by external excitations and/or strain engineering of a substrate.

Time dependence of current density, luminance, and efficiency under dc voltages for the thin-film electroluminescent device containing praseodymium and aluminum co-doped perovskite titanate phosphor

Time dependence of current density, luminance, and efficiency under dc voltages were measured for the thin-film electroluminescent device containing (Ca0.6Sr0.4)0.998Pr0.002Ti0.9Al0.1O3−δ phosphor in order to understand the electroluminescence mechanism. The current density was not zero and the luminance was close to zero immediately after voltages were applied to the device. Then, the current density and the luminance increased, reached a maximum, and decreased. The luminance and the efficiency did not recovered at room temperature but recovered at 400 °C. We proposed the band structures of the device depending on time due to electromigration of oxygen vacancies.

Effects of doping by aluminum or lanthanum on the electrical and electroluminescence properties of Ca0.6Sr0.4TiO3:Pr thin films

Thin-film electroluminescent devices containing Ca0.6Sr0.4TiO3:Pr, Al-doped Ca0.6Sr0.4TiO3:Pr, or La-doped Ca0.6Sr0.4TiO3:Pr phosphors were prepared by a conventional sol–gel and firing method. Doping by Al improved the performance of the device markedly, in that its current-starting voltage and emission-starting voltage decreased, its luminance response became more rapid, and its relative quantum efficiency increased. Almost all the effects of doping with La were opposite to those of doping with Al. On stacking thin films of Al-doped Ca0.6Sr0.4TiO3:Pr and La-doped Ca0.6Sr0.4TiO3:Pr, the current-starting voltage and the emission-starting voltages decreased further and the relative quantum efficiency increased further in comparison with the Al-doped film. The effects of doping by Al and La can be understood by assuming that Ca0.6Sr0.4TiO3:Pr separates into n-type and p-type semiconducting regions as a result of the electromigration of oxygen vacancies, and that the oxygen-vacancy density increases or decreases on doping by Al and La, respectively.

Insulation resistance degradation mechanisms of multilayer ceramic capacitors during highly accelerated temperature and humidity stress tests

The failure mechanisms of multilayer ceramic capacitors (MLCCs) with Ni internal electrodes under high temperature and high voltage conditions have been investigated through highly accelerated life tests (HALTs) in recent years. Generally, insulation resistance degradation during HALTs is presumed to be because of the electromigration of oxygen vacancies. Reliability in high-temperature, high-humidity, and rated-voltage environments is important for MLCCs. However, only a few studies have investigated the causes of insulation resistance degradation in MLCCs in these environments. We investigated the failure mechanisms of MLCCs through a highly accelerated temperature and humidity stress test. On the basis of presence of a degraded area on the anode side, we presumed that hydrogen ions were produced by H2O electrolysis at the interface between the ceramics and internal electrodes on the anode side, and that these hydrogen ions caused insulation resistance degradation.

Ultrafast collective oxygen-vacancy flow in Ca-doped BiFeO3

The ultrafast motion of oxygen vacancies in solids is crucial for various future applications, such as oxide electrolytes. Visualization and quantification can offer unforeseen opportunities to probe the collective dynamics of defects in crystalline solids, but little research has been conducted on oxygen vacancy electromigration using these approaches. Here, we visualize electric-field-induced creation and propagation of oxygen-vacancy-rich and -poor competing phases and their interface with optical contrast in Ca-substituted BiFeO3 that contains a high density of mobile oxygen vacancies. We quantitatively determined the drift velocity of collective migration to be on the order of 100 μm s−1 with an activation barrier of 0.79 eV, indicating a significantly large ionic mobility of 2 × 10−6 cm2 s−1 V−1 at a remarkably low temperature of 390 °C. In addition, visualization enables direct observation of fluidic behavior, such as the enhancement of conduction at channel edges, which results in U-shaped viscous propagation of the phase boundary and turbulence under a reverse electric field. All of these results provide new insights into the collective motion of defects.

(Invited) Liquid Electrolyte Contacts to Semiconductor Nanostructures: Probing and Programming Local Defect Behavior

Replacing the metal top electrode of a metal-insulator-semiconductor (MIS) or –metal (MIM) junction with a liquid electrolyte contact can be used 1) to study the capacitance and conductance response of semiconductor nanostructures with a conformal liquid contact, and 2) to program, at higher voltages, populations of point defects in an insulator layer, as a means of investigating local resistance switching. This presentation will summarize recent results on both of these topics, beginning with a discussion of electrochemical spectroscopy (EIS) applied to semiconductor-liquid junctions as a means of performing quantitative interface state characterization on micro- and nano-structured samples. Using aqueous KCl solution as a blocking contact to a semiconductor electrode, electrochemical impedance spectroscopy measures the multifrequency capacitance-voltage and conductance-voltage characteristics of planar p-Si (100), planar p-Si0.55Ge0.45 (100), and p-Si crystals with surfaces that are textured to create nanoscale features.1 These substrates are coated with thin atomic layer deposited Al2O3 dielectrics. Analysis of impedance data obtained from the planar samples produces results that are in good agreement with solid-state multi-frequency C-V and g-V data from the same sample, including similar extracted values for density of interface states. Impedance data and the extracted interface trap properties of ALD-Al2O3 passivated silicon microwire arrays for application in solar cells will also be described. Liquid electrolyte contacts have also been used to study resistance switching and its relation to local oxygen deficiency in an initially insulating metal oxide layer.2 Local variations in electrical conductivity in amorphous TiO2 films prepared by atomic layer deposition (ALD) are examined using conductive atomic force microscopy. The local TiO2 conductivity is correlated with changes in oxygen stoichiometry revealed by electron energy loss spectroscopy performed in the electron microscope and by oxygen isotope tracer exchange. Both highly resistive ionic liquids and highly conductive electrolyte solutions are used as liquid top contacts to the TiO2 layers. In this way, the effects of field-driven migration of oxygen ions in and out of the TiO2 film can be distinguished from local accumulation of oxygen vacancies via Joule heating at high programming currents. We find that gating using a resistive ionic liquid contact at room temperature and positive gate bias produces an oxygen deficient ALD-TiO2 film with enhanced electronic conductivity, demonstrating the ease with which field-driven oxygen vacancy formation occurs at low temperature in these thin amorphous layers. However, conductive filaments were formed only when the TiO2 is programmed using a lower-resistivity electrolyte top contact. This indicates the decisive importance of programming current in localization of the point defects required for filamentary conduction. C. Meng, K. Tang, M. Braun, L. Zhang, and P.C. McIntyre, “Electrochemical Impedance Spectroscopy for Quantitative Interface State Characterization of Planar and Nanostructured Semiconductor-Dielectric Interfaces,” Nanotechnol. 28, 415704 (2017). Tang, A.C. Meng, F. Hui, Y. Shi, T. Petach, C. Hitzman, A.L. Koh, D. Goldhaber-Gordon, M. Lanza, and P.C. McIntyre, “Distinguishing Oxygen Vacancy Electromigration and Conductive Filament Formation in TiO2 Resistance Switching Using Liquid Electrolyte Contacts,” Nano Lett. 17, 4390–99 (2017).

Distinguishing Oxygen Vacancy Electromigration and Conductive Filament Formation in TiO2 Resistance Switching Using Liquid Electrolyte Contacts.

Resistance switching in TiO2 and many other transition metal oxide resistive random access memory materials is believed to involve the assembly and breaking of interacting oxygen vacancy filaments via the combined effects of field-driven ion migration and local electronic conduction leading to Joule heating. These complex processes are very difficult to study directly in part because the filaments form between metallic electrode layers that block their observation by most characterization techniques. By replacing the top electrode layer in a metal-insulator-metal memory structure with easily removable liquid electrolytes, either an ionic liquid (IL) with high resistance contact or a conductive aqueous electrolyte, we probe field-driven oxygen vacancy redistribution in TiO2 thin films under conditions that either suppress or promote Joule heating. Oxygen isotope exchange experiments indicate that exchange of oxygen ions between TiO2 and the IL is facile at room temperature. Oxygen loss significantly increases the conductivity of the TiO2 films; however, filament formation is not observed after IL gating alone. Replacing the IL with a more conductive aqueous electrolyte contact and biasing does produce electroformed conductive filaments, consistent with a requirement for Joule heating to enhance the vacancy concentration and mobility at specific locations in the film.

Electric field control of the γ-Al2O3/SrTiO3 interface conductivity at room temperature

Controlling interfaces using electric fields is at the heart of modern electronics. The discovery of the conducting interface between the two insulating oxides LaAlO3 (LAO) and SrTiO3 (STO) has led to a number of interesting electric field-dependent phenomena. Recently, it was shown that replacing LAO with a spinel γ-Al2O3 (GAO) allows a good pseudo-epitaxial film growth and high electron mobility at low temperatures. Here, we show that the GAO/STO interface resistance, similar to LAO/STO, can be tuned by orders of magnitude at room temperature using the electric field of a backgate. The resistance change is non-volatile, bipolar, and can be tuned continuously rather than being a simple on/off switch. Exposure to light significantly changes the capabilities to tune the interface resistance. High- and low-resistive states are obtained by annihilation and creation, respectively, of free n-type carriers, and we speculate that electromigration of oxygen vacancies is the origin of the tunability.

Ferroelectric and flexible barrier resistive switching of epitaxial BiFeO3 films studied by temperature-dependent current and capacitance spectroscopy

The resistive switching of epitaxial ferroelectric BiFeO3 thin films was investigated by the combined current and capacitance spectroscopy, in addition with the piezoresponse force microscopy and conducting atomic force microscopy. A strong correlation between the resistance states and the capacitance states was found in the temperature range from 77 to 300 K, revealing the role of interface traps. It is demonstrated that the trap-assisted current transport contributes to the large ON current of the ferroelectric and flexible barrier resistive switching. The combination of ferroelectric polarization reversal, electromigration of oxygen vacancies, and interface traps leads to the nonvolatile memory performance with the ON/OFF ratio of 102 for >105 s and the endurance of over 8000 cycles at room temperature.

Visible-light-accelerated oxygen vacancy migration in strontium titanate.

Strontium titanate is a model transition metal oxide that exhibits versatile properties of special interest for both fundamental and applied researches. There is evidence that most of the attractive properties of SrTiO3 are closely associated with oxygen vacancies. Tuning the kinetics of oxygen vacancies is then highly desired. Here we reported on a dramatic tuning of the electro-migration of oxygen vacancies by visible light illumination. It is found that, through depressing activation energy for vacancy diffusion, light illumination remarkably accelerates oxygen vacancies even at room temperature. This effect provides a feasible approach towards the modulation of the anionic processes. The principle proved here can be extended to other perovskite oxides, finding a wide application in oxide electronics.