V2O5 Content Research Articles

Decoupling many-body interactions in the CeO2(111) oxygen vacancy structure with statistical learning and cluster expansion.

Oxygen vacancies (VO's) are of paramount importance in influencing the properties and applications of ceria (CeO2). Yet, comprehending the distribution and nature of VO's poses a significant challenge due to the vast number of electronic configurations and intricate many-body interactions among VO's and polarons (Ce3+ ions). In this study, we established a cluster expansion model based on first-principles calculations and statistical learning to decouple the interactions among the Ce3+ ions and VO's, thereby circumventing the limitations associated with sampling electronic configurations. By separating these interactions, we identified specific electronic configurations characterized by the most favorable VO-Ce3+ attractions and the least favorable Ce3+-Ce3+/VO-VO repulsions, which are crucial in determining the stability of vacancy structures. Through more than 108 Metropolis Monte Carlo samplings of VO's and Ce3+ ions in the near surface of CeO2(111), we explored potential configurations within an 8 × 8 supercell. Our findings revealed that oxygen vacancies tend to aggregate and are abundant in the third oxygen layer with an elevated VO concentration primarily due to extensive geometric relaxation, an aspect previously overlooked. This work introduces a novel theoretical framework for unraveling the complex vacancy structures in metal oxides, with potential applications in redox and catalytic chemistry.

Effect of the content of V2O5 on the thermal conductivity of diamond/Cu composites prepared by spark plasma sintering

Effect of the content of V2O5 on the thermal conductivity of diamond/Cu composites prepared by spark plasma sintering

Effect of crystalline TiO2 on V2O5WO3/TiO2 as tunable low-temperature shift De-NOx catalyst

Based on the crystalline size of anatase TiO2, a series of tunable low-temperature shift V2O5-WO3/TiO2 (VW/Ti) catalysts for NH3 selective catalytic reduction (NH3-SCR) of NOx were prepared by impregnation process. These catalysts contained a loading amount of 2 wt% WO3 and either 2 or 5 wt% V2O5. The tunable low-temperature shift De-NOx performance of the VW/Ti catalysts was significantly enhanced and dramatically decreased after heat treatment of TiO2 from 100 °C to 700 °C (Ti100–Ti700). Nearly 100 % De-NOx efficiency was achieved at a gas hourly space velocity (GHSV) of 60,000 h−1. A notable shift from higher to lower temperatures was observed from V2W2/Ti100 to V2W2/Ti600; however, the activity was lost for V2W2/Ti650 to V2W2/Ti700. When the V2O5 loading increased from 2 wt% to 5 wt%, the V5W2/Ti600 showed the highest De-NOx efficiency at 225 °C, demonstrating a remarkable synergistic effect compared to the V2W2/Ti100 catalyst, which achieved maximum efficiency at 375 °C. The De-NOx performance and low-temperature shift effect of these catalysts were elucidated by considering TiO2 crystalline size, the synergistic effect between V2O5 content and TiO2, and the V4+/V5+ oxidation state of V2O5 in the catalyst. Additionally, the high crystalline TiO2-based V2W2/Ti600 catalyst prepared in this study is expected to effectively decompose NOx at low temperatures, in contrast to the low crystalline TiO2-based V2W2/Ti100 catalyst.

Unraveling the Effect of Oxygen Vacancy on WO3 Surface for Efficient NO2 Detection at Low Temperature.

Oxygen vacancies (VO) in metal oxide semiconductors play an important role in improving gas-sensing performance of chemiresistive gas sensors. Nonetheless, there is still a lack of clear understanding of the inherent mechanism of the influence of oxygen vacancies on gas sensing due to generally focusing on the concentration of VO. Herein, oxygen vacancies were rationally modulated in WO3 nanoflower structures via an annealing process, resulting in a transformation of VO from neutral (VO0) to a doubly ionized (VO2+) state. Density functional theory (DFT) calculations indicate that VO2+ is significantly more efficient than VO0 for NO2 detection in competition with atmospheric O2. Benefiting from a high concentration of VO2+, the WO3-450 (WO3 annealed at 450 °C) sensor exhibits excellent sensing performance with an ultrahigh sensitivity (3674.1 to 5 ppm NO2), superior selectivity, and long-term stability (one month). Furthermore, the sensor with the wide range of concentration detection not only can detect NO2 gas with parts per million (ppm) but also can detect NO2 with parts per billion (ppb) level concentration, with a high sensibility reaching 2.8 to 25 ppb NO2 and over 100 to 100 ppb NO2. This study elucidates the oxygen vacancy mediated sensing mechanism toward NO2 and provides an effective strategy for the rational design of gas sensors with high sensing performance.

A Sustainable Recycling Route from Spent Sulfuric Acid Catalysts to Vanadium Pentoxide Precursor for the Production of Low‐Cost Na3V2(PO4)3@C Na‐Ion Batteries

AbstractThe extraction of vanadium from spent industrial catalysts is a widely practiced process globally due to the large quantities of material available with appreciable vanadium content. However, some of these spent catalysts are unresponsive to established extraction methods because they have different properties. Therefore, separate studies are necessary to deal with specific cases. This work demonstrates how the leaching step can limit the recovery of vanadium to the solution before the coprecipitation step. The NH4Cl‐H2SO4synergetic system achieved a high vanadium leaching rate of up to 95 %, resulting in the preparation of high‐purity NH4VO3with 75.45 % V2O5content. This demonstrates the potential of the prepared V2O5as a precursor for vanadium materials used in sodium‐ion batteries, allowing for the adjustment of the valence of vanadium. The Na3V2(PO4)3@C particles exhibit a discharge capacity of 110 mAh g−1at a current density of 0.1 C and 90 mAh g−1at 1 C. The synergistic leaching system provides a sustainable method for the recovery and reuse of vanadium from spent vanadium catalysts. This contributes to recycling efforts and the development of sodium‐ion batteries.

Experimental study and DFT+U calculations on the impact of Rare-Earth ion (La3+, Sm3+, Y3+, Yb3+) doped CeO2 Core-Shell abrasives on polishing performance

A series of carbon spheres coated with Rare-Earth ion-doped (La3+, Sm3+, Y3+, Yb3+) CeO2 (CS@CeO2) were synthesized using eco-friendly hydrothermal and chemical precipitation methods. The structural characteristics of the abrasives were thoroughly analyzed using XRD, SEM, TEM, and FT-IR techniques. A detailed analysis of Ce3+ and Vo concentrations on the CeO2 layer surface was conducted using XPS and Raman spectroscopy. The analysis results indicated that CS@Ce0.9Y0.1O2 abrasives exhibited the highest Ce3+ (46.23 %) and Vo (25.39 %) concentrations. Additionally, the polishing performance of the abrasives was evaluated using atomic force microscopy (AFM). The CS@Ce0.9Y0.1O2 abrasive exhibited superior polishing performance, achieving the lowest surface roughness (Ra = 0.26 nm) compared to commercial abrasives (Ra = 0.77 nm), reducing Ra by 66.23 %. Moreover, density functional theory with the Hubbard U method (DFT+U) was used to systematically investigate the oxygen vacancy formation energy, structural stability, and electronic properties of CeO2 doped with Rare-Earth ions. These findings demonstrate that doping with Rare-Earth ions possessing ionic radii close to that of Ce4+ effectively enhances the concentration of oxygen vacancies and Ce3+ ions, which is crucial for improving polishing performance. This work provides valuable reference data on the doping of Rare-Earth ions in CeO2-based polishing abrasives.

Spectral analysis and characterization of Na2O-SiO2-ZrO2 glasses doped with V2O5

Na2O-SiO2-ZrO2 glasses doped with V2O5 were prepared with the melt quenching method, and were then analyzed using various techniques; in particular, with X-ray diffraction (XRD), energy dispersive spectroscopy (EDS), and optical absorption, photoluminescence, electron spin resonance (ESR), and Fourier transform infrared (FT-IR) transmission spectroscopy. The obtained results indicate that, in the studied glasses, vanadyl complexes tend to undergo a reduction from V5+ ions to V4+ ions. XRD and EDS data suggest that the glasses have amorphous nature with randomly distributed grains within the glass matrix. The optical absorption spectra show two transitions: 2B2g→2B1g and 2B2g→2Eg. The photoluminescence spectra exhibit a broad band from 750-900 nm, indicating the 2E→2T2 transition of vanadyl ions. The energies of the band gaps decreased gradually with increasing V2O5 content. The ESR spectra suggest that V4+ ions are situated in octahedral sites with tetragonal compression. The FT-IR spectra confirm the presence of various structural units within the glasses. Finally, the dielectric properties of the glasses were also measured, showing that the dielectric constant (ε′) and the loss tangent (tan δ) increase as the content of vanadium ions increases, indicating presence of V4+ ions within the glass matrix.

Efficient photocatalytic degradation of diclofenac drug using the Zn1-x-yPrxAlyO photocatalyst under UV light irradiation.

Herein, we report the efficient photocatalytic degradation of the diclofenac drug using the Zn1-x-yPrxAlyO photocatalyst [x, y] = (0.00, 0.00), (0.03, 0.01), (0.03,0.03) under UV light irradiation. The analysis of the structure reveals that the Pr3+ and Al3+ cations insertion into the ZnO lattice leads to a decrease in the lattice constant (a and c), Zn-O bond length, strain lattice, and crystallite size. These alterations are linked to the high degree of atomic disorder triggered by the dopants, which produce stress and strain in the ZnO structure. The Raman measurements confirmed the structural phase and showed changes in the position and intensity of the E2High mode, associated with oxygen vibrations and material crystallinity. The presence of the dopants reduces the concentration of VZn and VO++ type defects while increasing the levels of VO, VO+, and Oi defects, as observed from the fitting of the Photoluminescence spectra. Furthermore, it was noted that de Pr3+ and Al3+ cations insertion into ZnO increases the optical band gap, which is associated with the Moss-Burstein effect. The micrograph images show that dopants transform the morphology from quasi-spherical particles to irregular cluster structures. The textural analysis indicated that an increase in the concentration of Al3+ in the ZnO lattice led to a higher surface area, likely enhancing photocatalytic activity. The sample containing 3% Pr3+ and 3% Al3+ showed the highest photocatalytic activity and degraded up to 71.42% of diclofenac. In addition, experiments with scavengers revealed that hydroxyl radicals are the main species involved in the drug's photodegradation mechanism. Finally, the Zn1-x-yPrxAlyO compound is highly recyclable and stable.

Oxygen vacancy engineering in Si-doped, HfO2 ferroelectric capacitors using Ti oxygen scavenging layers

In this paper, the ferroelectric properties of TiN/Ti/Si:HfO2/TiN stacks are shown to be modulated by the Ti oxygen scavenging layer, leading to improved remanent polarization and wake-up at low switching fields. Hard x-ray photoelectron spectroscopy is used to measure the oxygen vacancy (VO) concentration in Si-doped HfO2 based capacitors. This VO engineered ferroelectric stack is then assessed at the wafer scale within 16 kbit 1T-1C FeRAM arrays integrated into 130 nm CMOS. The introduction of a Ti oxygen scavenging layer at the top interface of Si:HfO2-based BEOL-integrated metal/ferroelectric/metal capacitors enhances their ferroelectric (FE) behavior (+100% remanent polarization 2.Pr), confirming the positive role of modest concentrations of VO in orthorhombic phase crystallization at low thermal budgets. It is statistically demonstrated at 16 kbit array level that VO-rich FE Si:HfO2 facilitates 2.5 V FeRAM array operation with improved memory window. The field cycling dependence of the memory window is correlated with the VO concentration, and an endurance of 108 cycles is measured at the array level.

Size-Dependent Oxygen Vacancy of Iron Oxide Nanoparticles.

Prior research has highlighted the reduction of iron oxide nanoparticle (IONPs) sizes to the "ultra-small" dimension as a pivotal approach in developing T1-MRI contrast agents, and the enhancement in T1 contrast performance with the reducing size is usually attributed to the increased specific surface area and weakened magnetization. Nonetheless, as the size decreases, the variation in surface defects, particularly oxygen vacancy (VO) defects, significantly impacts the T1 imaging efficacy. In this study, the VO on IONPs is meticulously investigated through XPS, Raman, and EPR spectroscopy. As the nanoparticle size decreased, the VO concentration rose initially but subsequently declined, with the peak concentration observed in the size of 8.27nm. Further insights gained from synchrotron XAS analysis and DFT calculations indicate that both surface tension and phase transition in IONPs contribute to alterations in the Fe─O bond length, thereby influencing the VO formation energy across varying nanoparticle sizes. The MRI tests reveal that the VO in IONPs serve as pivotal sites for the attachment of water molecules to iron ions, and IONPs with fewer VO exhibited a deterioration in T1-MRI contrast effects. This research may provide a deeper understanding of the relationship between T1 contrast performance and the size of IONPs.

P‐12: Improve the Reliability of a‐IGZO TFT through Optimizing the Threshold Voltage and Channel Thickness in AMOLED Hybrid Backplane

In the fabrication of flexible a‐IGZO and LTPS thin film transistor (TFT) hybrid backplane, various threshold voltage (Vth) of the a‐IGZO TFT was achieved in this paper by regulating the O2/Ar ratio during the deposition of a‐IGZO film by sputtering. The results show that the Vth increases with the increase of the O2/Ar ratio, and the reliability tests indicate that in a certain range negative adjustment of Vth can significantly improve the positive bias temperature instability (PBTI) of IGZO TFT, and maintain good electrical uniformity. The increase of the O2/Ar ratio reduces the number of oxygen vacancy (Vo) in the a‐IGZO channel, and thereby Vth is positively shifted, which is confirmed by the TCAD simulation. The Vth value can indicate the Vo concentration in a‐IGZO TFT channel partly, and appropriately higher amount of Vo is beneficial to improve the PBTI, which is attributed to Fermi level (EF) shifting closer to conduction band. Raised EF means less unoccupied trap states, resulting in less carrier trapping under PBTI. Furthermore, the research also explores different a‐IGZO channel thicknesses and finds that when the Vth values are similar, thinner channel layers endow a‐IGZO TFT with improved PBTI. By optimizing the Vth and channel thickness, a‐IGZO TFTs with a channel thickness of 25nm and a Vth value of 0.2V have been prepared in a hybrid backplane. Under positive bias temperature stress for 5 hours, the Vth is positively shifted less than 0.5 V, which could lay the foundation for achieving high‐reliability flexible backplane for AMOLEDs.

Tuning the band gap, optical, mechanical, and electrical features of a bio-blend by Cr2O3/V2O5 nanofillers for optoelectronics and energy applications

This work presents a facile approach for controlling the optical and electrical parameters of a biopolymeric matrix for optoelectronics. Vanadium oxide (V2O5) and chromium oxide (Cr2O3) nanoparticles (NPs) were prepared and incorporated into the carboxymethylcellulose/polyethylene glycol (CMC/PEG) blend by simple chemical techniques. Transmission electron microscopy (HR-TEM), and X-ray diffraction (XRD) data showed that V2O5 and Cr2O3 exhibited spherical shapes with sizes in the range of 40–50 nm and 10–20 nm, respectively. In addition, the blend's degree of crystallinity was sensitive to the V2O5 and Cr2O3 doping ratios. The scanning electron microscopy (FE-SEM) and the elemental chemical analysis (EDAX) used to study the filler distribution inside the blend, and confirmed the existence of both V and Cr in the matrix. Fourier transform infrared (FTIR) spectroscopy showed that the dopants significantly affected the blend reactive (C–O–C, OH, and C=O) groups. The stress–strain curves illustrated the reinforcing effect of the dopants up to 1.0 wt\\%\\documentclass[12pt]{minimal} \\usepackage{amsmath} \\usepackage{wasysym} \\usepackage{amsfonts} \\usepackage{amssymb} \\usepackage{amsbsy} \\usepackage{mathrsfs} \\usepackage{upgreek} \\setlength{\\oddsidemargin}{-69pt} \\begin{document}$$\ ext{wt\\%}$$\\end{document} Cr2O3/V. The transmittance and absorption index spectra in the visible-IR wavelengths decreased with increasing filler content. Utilizing Tauc's relation and (optical) dielectric loss, the direct (indirect) band gap narrowed from 5.6 (4.5) eV to 4.7 (3.05) eV at 1.0 wt\\%\\documentclass[12pt]{minimal} \\usepackage{amsmath} \\usepackage{wasysym} \\usepackage{amsfonts} \\usepackage{amssymb} \\usepackage{amsbsy} \\usepackage{mathrsfs} \\usepackage{upgreek} \\setlength{\\oddsidemargin}{-69pt} \\begin{document}$$\ ext{wt\\%}$$\\end{document} Cr2O3/V. All films have an index of refraction in the range of 1.93–2.17. AC conductivity was improved with increasing filler content and temperature. The energy density at 50 °C is in the range of 1–3 J/m3. The influence of V2O5 and Cr2O3 content on the optical conductivity, dielectric constant, loss, and dielectric modulus of CMC/PEG was reported. These enhancements in electrical and optical properties, along with the potential for band gap engineering, offer promising prospects for advanced applications in optoelectronics and energy-related fields.

An Investigation of Selective Catalytic Reduction Catalyst SO2/SO3 Conversion in Coal-fired Power Plants

The SO2/SO3 conversion in the selective catalytic reduction (SCR) denitrification system of coal-fired power plants plays a significant role in the generation of SO3. Effectively controlling the conversion rate of SO2/SO3 in the denitrification catalyst can substantially mitigate the hazards associated with SO3. Drawing on 170 SCR catalyst tests, the impact of various factors, including the catalyst’s V2O5 content, WO3/MoO3 content, inlet SO2 concentration, inlet flue gas temperature, and area velocity, on the SO2/SO3 conversion was systematically investigated. The findings suggest potential optimization opportunities for the SO2/SO3 conversion rate in the denitrification catalysts currently used in engineering applications. By understanding the influence patterns of key factors, tailored measures such as selecting appropriate performance indicators, designing catalysts for specific projects, and adjusting key operational parameters in coal-fired power plants can be implemented. These measures are aimed at preventing problems like corrosion and blockage in downstream facilities due to SO3 and effectively controlling SO3 emissions.

Structure–polaronic conductivity relationship in vanadate–phosphate glasses

AbstractThis work provides new insights into the nature of the polaronic transport in xV2O5–(100−x)P2O5, 41 ≤ x ≤ 89 mol% glasses from analysis of their conductivity over a wide range of frequencies and temperatures, and correlation of the electrical parameters to the structural models of these materials. The results show that the linear increase in direct current (DC) conductivity with the increase in V2O5 could be related to the formation of a vanadate subnetwork, which is characterized by a length distribution of V–O bonds and variations in linkages between different vanadate units. Such a structurally complex network offers multiple conduction pathways which are favorable for polaron hopping. The Summerfield scaling of conductivity spectra reveals a temperature‐invariant mechanism of polaron transport for all glasses and the same local structural environment of polarons at higher V2O5 contents due to the same ratio of vanadate units present in the network. Also, this study highlights the similarities and differences in the nature of the polaronic transport of vanadate–phosphate glasses and other polaronically conducting phosphate glasses containing WO3, MoO3, and Fe2O3, and pins down a pivotal role of the glass structure in electrical processes in these materials.

High-performance Ga2O3 solar-blind UV photodetectors via film growth regulation and surface state engineering

Gallium oxide (Ga2O3) with a wide bandgap is emerging as one of the most promising candidates for solar-blind photodetectors (SBPDs). However, the practical application of Ga2O3-based SBPDs is impeded by substantial defects-related leakage currents, sluggish response speed, and high-cost, making their practical applications face great challenges. Here, we proposed strategic films growth regulation and surface state engineering to grow high-quality yet economical β-Ga2O3 films, thereby achieving high-performance SBPDs. High-resolution transmission electron microscopy revealed the presence of high-quality films with an extremely regular arrangement of β-Ga2O3 (2‾01) planes. The full width at half maximum and root mean square roughness values are 0.07° and 0.716 nm, respectively. The β-Ga2O3 films demonstrated a significant reduction in VO concentrations after O2/N2 plasma treatment. This process can effectively minimize thermal damage to the sample surface while retaining highly reactive free radicals. The photocurrents of devices can be further enhanced, leading to a larger PDCRs of 8.6 × 107, through N2 plasma treatment. Moreover, the films effectually suppress the persistent photoconductivity effect with τr and τd values of 5.31/0.97 s and 0.49/0.87 s before and after N2 plasma treatment, respectively. We have demonstrated the influence mechanism of O2/N2 plasma treatment on photoelectronic performance. This study provides a practical approach to growing high-quality β-Ga2O3 films and preparing high-performance but low-cost Ga2O3-based SBPDs.

Fluorinated silane self-assembled monolayer modification of V2O5 for enhanced hole injection and device efficiency

This study introduces a new approach to enhance hole injection in organic light-emitting diodes (OLEDs) by modifying the energy band alignment. This enhancement is achieved by incorporating gap states near the Fermi level through the application of a 1H,1H,2H,2H-perfluorooctyltriethoxysilane self-assembled monolayer (F8SAM) coating on V2O5. Compared to thermally evaporated V2O5, the F8SAM coating induces greater oxygen deficiency, reducing the V2O5 (V5+) content from 84.2 % to 76.9 % and increasing the VO2 (V4+) content from 15.7 % to 23.0 %. This modification causes both the highest occupied molecular orbital and gap state levels to move closer to the Fermi level, facilitated by increased oxygen vacancies, high carrier concentration, and delocalized free electrons. The alteration in the gap state provides a more accessible pathway for efficient hole injection, as confirmed in optoelectronic green light devices, which demonstrate a wavelength of 530 ± 5 nm. Significantly, devices incorporating a double-layer hole-injection layer exhibit a 5-fold increase in maximum luminance, a 1.6-fold increase in current efficiency, and a 1.7-fold increase in power efficiency compared to devices with an unmodified V2O5 film. The enhanced performance is attributed to the well-aligned F8SAM on V2O5, which increases the density of hole states and thereby improves device performance. This study demonstrates a practical method for modulating the cation valence state of V2O5, offering a pathway toward improved hole injection and, consequently, more efficient and functional OLED devices.

Effect of RF power on analog synaptic behavior of sputter-deposited InGaZnO films for neuromorphic computing applications

We demonstrate that an analog synaptic weight update can be achieved using identical pulses via gradual resistance switching of memristors based on sputter-deposited InGaZnO (IGZO) films. When a positive voltage is applied to the IGZO memristor, oxygen vacancies (Vo) are ionized and electrons that serve as dopants are generated. This lowers the Schottky barrier formed at the interface and decreases the resistance. However, a negative voltage provides electrons from the Pd electrode, annihilating the ionized vacancies. As the barrier is reconstructed, the IGZO memristor exhibits a high-resistance state (HRS). As Vo plays a crucial role in switching, the effect of the radio frequency (RF) power on the memristor during the IGZO deposition is examined. A physical analysis reveals that the Vo concentration in the IGZO is proportional to the RF power, inducing a leaky HRS. However, at the expense of a reduced memory window in the IGZO deposited at a higher power of 200 W, the resultant low-resistance state is reliable over time. The strengthened retention allows the synaptic weights to be linearly decreased even by consecutive negative pulses. Hence, when the IGZO memristors are used for synaptic elements to construct neural networks, a higher recognition accuracy for the MNIST dataset is achieved.

Tuning grain boundary cation segregation with oxygen deficiency and atomic structure in a perovskite compositionally complex oxide thin film

Compositionally complex oxides (CCOs) are an emerging class of materials encompassing high entropy and entropy stabilized oxides. These promising advanced materials leverage tunable chemical bond structure, lattice distortion, and chemical disorder for unprecedented properties. Grain boundary (GB) and point defect segregation to GBs are relatively understudied in CCOs even though they can govern macroscopic material properties. For example, GB segregation can govern local chemical (dis)order and point defect distribution, playing a critical role in electrochemical reaction kinetics, and charge and mass transport in solid electrolytes. However, compared with conventional oxides, GBs in multi-cation CCO systems are expected to exhibit more complex segregation phenomena and, thus, prove more difficult to tune through GB design strategies. Here, GB segregation was studied in a model perovskite CCO LaFe0.7Ni0.1Co0.1Cu0.05Pd0.05O3−x textured thin film by (sub-)atomic-resolution scanning transmission electron microscopy imaging and spectroscopy. It is found that GB segregation is correlated with cation reducibility—predicted by an Ellingham diagram—as Pd and Cu segregate to GBs rich in oxygen vacancies (VO··). Furthermore, Pd and Cu segregation is highly sensitive to the concentration and spatial distribution of VO·· along the GB plane, as well as fluctuations in atomic structure and elastic strain induced by GB local disorder, such as dislocations. This work offers a perspective of controlling segregation concentration of CCO cations to GBs by tuning reducibility of CCO cations and oxygen deficiency, which is expected to guide GB design in CCOs.

Effects of firings in hydrogen on the insulation performances of a 95 wt% alumina ceramic

To investigate the effects of point defects on the insulation performances of alumina ceramics, we fire a 95 wt% alumina ceramic in wet hydrogen, dry hydrogen, and supplementary air, to change the concentrations of aluminum vacancy (VAl‴) and oxygen vacancy (VO••). The dielectric breakdown strength (DBS) and flashover voltage (FV) are tested, and the point defects are characterized by XPS and optical reflectance. Firing in wet hydrogen decreases the concentration of VO••, improving DBS but deteriorating FV. Nevertheless, firing in dry hydrogen increases the concentration of VAl‴, improving FV but deteriorating DBS. Supplementary firing in air weakens the effects of firing in dry hydrogen on the point defects and insulation performances. The effects of firings on insulation performances are attributed to the concentrations of electrical carriers that are determined by the point defects, and this is confirmed by the results of electrical resistivity.

Atomic-scale oxygen-vacancy engineering in Sub-2 nm thin Al2O3/MgO memristors

Ultrathin (sub-2 nm) Al2O3/MgO memristors were recently developed using an in vacuo atomic layer deposition (ALD) process that minimizes unintended defects and prevents undesirable leakage current. These memristors provide a unique platform that allows oxygen vacancies (VO) to be inserted into the memristor with atomic precision and study how this affects the formation and rupture of conductive filaments (CFs) during memristive switching. Herein, we present a systematic study on three sets of ultrathin Al2O3/MgO memristors with VO-doping via modular MgO atomic layer insertion into an otherwise pristine insulating Al2O3 atomic layer stack (ALS) using an in vacuo ALD. At a fixed memristor thickness of 17 Al2O3/MgO atomic layers (∼1.9 nm), the properties of the memristors were found to be affected by the number and stacking pattern of the MgO atomic layers in the Al2O3/MgO ALS. Importantly, the trend of reduced low-state resistance and the increasing appearance of multi-step switches with an increasing number of MgO atomic layers suggests a direct correlation between the dimension and dynamic evolution of the conducting filaments and the VO concentration and distribution. Understanding such a correlation is critical to an atomic-scale control of the switching behavior of ultrathin memristors.