3D Oxide Research Articles

(Invited) Plasmon and Polaritons in Two-Dimensional Molybdenum Compounds

Plasmonics and polarotonics of two dimensional (2D) materials have attracted significant attention due to their desirable dispersion relation. Regarding plasmons, according to the 2D dispersion equation, the cutoff frequency limit can be eliminated. Additionally, their large tuneability, high doping (ultradoping) range, and the existence of favorable depolarization factors allow for their better control. Among 2D materials, molybdenum disulfides and molybdenum oxides have recently received increased attention.1-5 The polariton propagation has also been recently shown in atomically smooth molybdenum oxides. For plasmonic propagatrions, tunable plasmon resonances in suspended 2D molybdenum oxide and molybdenum sulfide flakes are demonstrated. The 2D configuration generates a large depolarization factor and the presence of ultra-doping produces visible-light plasmon resonances. The ultra-doping process is conducted by reducing the semiconducting 2D molybdenum trioxide flakes using simulated solar irradiation. The generated plasmon resonances are controlled by the doping levels and the flakes’ lateral dimensions, as well as by exposure to model proteins and enzymes. It is also possible to reach ultradoping levels. Alternatively, by electrochemically intercalating lithium into 2D molybdenum disulfide nanoflakes, plasmon resonances in the visible and near UV wavelength ranges are achieved. These plasmon resonances are controlled by the high doping level of the nanoflakes after the intercalation, producing two distinct resonance peak areas based on the crystal arrangements. The system is also benchmarked for biosensing using bovine serum albumin. The talk will provide the foundation for developing future 2D molybdenum sulphide and oxide based biological and optical units. Polaronic propagation in full stoichiometric molybdenum oxides will also be discussed.6 References 1 Zhang, B. Y.; Zavabeti, A.; Chrimes, A. F.; Haque, F.; O'Dell, L. A.; Khan, H.; Syed, N.; Datta, R.; Wang, Y.; Chesman, A. S. R.; Daeneke, T.; Kalantar-zadeh, K.; Ou, J. Z.,. Advanced Functional Materials 2018, 28, 1706006. 2 Wang, Y.; Ou, J. Z.; Chrimes, A. F.; Carey, B. J.; Daeneke, T.; Alsaif, M. M. Y. A.; Mortazavi, M.; Zhuiykov, S.; Medhekar, N.; Bhaskaran, M.; Friend, J. R.; Strano, M. S.; Kalantar-Zadeh, K., Nano Letters 2015, 15, 883-890. 3 Ma, W.; Alonso-González, P.; Li, S.; Nikitin, A. Y.; Yuan, J.; Martín-Sánchez, J.; Taboada-Gutiérrez, J.; Amenabar, I.; Li, P.; Vélez, S.; Tollan, C.; Dai, Z.; Zhang, Y.; Sriram, S.; Kalantar-Zadeh, K.; Lee, S. T.; Hillenbrand, R.; Bao, Q., Nature 2018, 562, 557-562. 4 de Castro, I. A.; Datta, R. S.; Ou, J. Z.; Castellanos-Gomez, A.; Sriram, S.; Daeneke, T.; Kalantar-zadeh, K., Advanced Materials 2017, 29, 1701619. 5 Alsaif, M. M. Y. A.; Latham, K.; Field, M. R.; Yao, D. D.; Medhekar, N. V.; Beane, G. A.; Kaner, R. B.; Russo, S. P.; Ou, J. Z.; Kalantar-Zadeh, K., Advanced Materials 2014, 26, 3931-3937. 6 Ma W.; Alonso-González, P.; Li, S.; Nikitin, A.W.; Yuan, J.; Martín-Sánchez, J.; Taboada-Gutiérrez, J.; Amenabar, I.; Li, P., Vélez, S.; Tollan, C.; Dai, Z.; Zhang, Y.; Sriram, S.; Kalantar-Zadeh, K.; Lee. S-T., Hillenbrand, R.; Bao, Q. Nature 2018, 562, 557-562.

Solution-Based Synthesis of Layered Two-Dimensional Oxides as Broadband Emitters.

Preparing transition-metal oxides in their two-dimensional (2D) form is the key to exploring their unrevealed low-dimensional properties, such as the p-type transparent superconductivity, topological Mott insulator state, existence of the condensed 2D electron/hole gas, and strain-tunable catalysis. However, existing approaches suffer from the specific constraint techniques and precursors that limit their product types. Here, we report a solution-based method to directly synthesize KNbO2 in 2D by an out-of-the-pot growth process at low temperature, which is observed directly in real time. The developed method can also be applied to other 2D ternary oxide syntheses, including CsNbO2 and composited NaxK1-xNbO2, and it can be extended to the preparation of self-assembled nanofilms. In addition, We demonstrate the emission of broadband photoluminescence (PL, λ ∼ 350-800 nm) from as-synthesized single-crystal 2D KNbO2 sheets down to a single unit cell thickness. The ultra-broadband emission is ascribed to the self-trapped excitation state (STEs) from the in-phase distortion of the NbO6 octahedrons in 2D NbO2- layers. Beyond the broader luminescent range and the robust material thermal stability of niobates, the absence of sample size restrictions and the large aspect ratio of the 2D oxide sheets will provide opportunities in miniaturizing and advancing 2D-materials integrated optoelectronic devices.

Two-dimensional SnO ultrathin epitaxial films: Pulsed laser deposition growth and quantum confinement effects

Two-dimensional (2D) ultrathin oxides are crucial for modern quantum electronic devices. However, the well-controlled growth of 2D oxide materials is highly challenging. In this work, ultrathin single-crystal SnO epitaxial films were achieved on r-sapphire by pulsed laser deposition. The quasi-2D SnO films have thicknesses ranging from 3.4 to 25.4 nm, allowing observation of quantum confinement effects in the optical bandgap. The critical thickness where the films relax in plane is around 19 nm. Below 19 nm, the films are strained compressively in plane and tensilely along the c-axis. Quantum confinement effects are observed by UV-IR spectroscopy for the optical transition at the direct bandgap. By fitting Brus equation, the reduced effective mass is deduced to be 0.137 ± 0.016 me. The exciton radius and binding energy are 4.62 ± 0.61 nm and 10.8 ± 1.2 meV, respectively. These parameters are crucial for the design and application of SnO-based quantum devices.

2-Mercaptobenzimidazole films formed at ultra-low pressure on copper: adsorption, thermal stability and corrosion inhibition performance

2-mercaptobenzimidazole (2-MBI) is considered as an effective corrosion inhibitor for copper. In this study, the adsorption of 2-MBI on pristine and pre-oxidized Cu(111) surfaces was investigated by sublimation at ultra low pressure, using Auger Electron Spectroscopy, Scanning Tunneling Microscopy and X-ray Photoelectron Spectroscopy in order to understand its corrosion inhibition properties. 2-MBI adsorbs with S and N atoms bonded to Cu. On pristine Cu(111) surface, a self-assembled monolayer is formed at about 5 L, with the adsorption of atomic S resulting from molecule decomposition to form a (7×7)R19.1° structure, and that of the molecule forming a (8 × 8) structure. 2-MBI is lying flat in the adsorbed multilayer. Oxidation of copper prior to exposure results in compact and homogeneous molecular films, with dissociation and substitution of 2D oxide by 2-MBI, but much more slower than that for 2-mercaptobenzothiazole (2-MBT). A multilayer of 2-MBI can block the initial stages of oxidation of copper under low oxygen pressure at room temperature, and the molecular layer is stable until 500°C. The comparison with 2-MBT suggests that the latter is a better corrosion inhibitor for copper at room temperature.

(Invited) Where Are the Best Insulators for 2D Field-Effect Transistors?

Two-dimensional (2D) semiconductors are very promising for applications in next-generation field-effect transistors (FETs) which could overcome scaling limitations of Si technologies and thus extend the life of Moore’s law. The success at achieving this ambitious goal will depend on the availability of compatible insulators which are always required to separate the gate from the channel. Ideally, these insulators should go along with 2D semiconductors as well as SiO2 goes with Si. However, the research community is mostly focused on 2D semiconductors while not paying enough attention to finding suitable insulators for 2D FETs. In order to shed some light on this problem, here we formulate general requirements for insulators in 2D FETs and discuss the potential of already used and promising materials.The scaling potential of 2D FETs can be fully exploited only if high quality insulators with an equivalent oxide thickness (EOT) below 1nm are available, as required for low subthreshold swings and reduced power consumption. This results in the following requirements for gate insulators: First, dielectric properties have to be good enough to maintain low tunnel and thermionic leakage currents to achieve high on/off current ratios. This implies high dielectric constants, wide band gaps and large band offsets with the channel material. Second, the insulator must form a well-defined interface with the channel, which is primarily required for a high mobility. Third, the number of active insulator defects within a few nanometers from the interface has to be low, in order to reduce charge trapping and thus maintain high stability of device operation. Finally, the insulators have to be electrically stable when scaled and survive electric fields of at least 10MV/cm.Most previously reported 2D FETs employ conventional oxides (e.g. SiO2, HfO2, Al2O3) known from Si technologies. High-k oxides HfO2 and Al2O3 appear to be the most promising, as they in principle satisfy the requirement on low leakage currents. However, they are amorphous when grown in thin layer, thus forming poor-quality interfaces with 2D channels, and contain numerous unavoidable insulator defects which lead to hysteresis and long-term drifts of the gate transfer characteristics. As a result, it appears to be unlikely that these materials can be considered promising for applications in future fully scalable 2D FETs.In the spirit of Si technologies, a possible alternative to conventional oxides could be oxidation of 2D semiconductors to form native oxides, such as MoO3 from MoS2. While this may improve the interface quality, native oxides are still amorphous and sometimes non-stoichiometric, which leads to high densities of insulator defects and limited electric strength. Thus, considerable research efforts are still required to understand their potential.Another possible solution is the use of layered 2D insulators. Their main advantage is their crystalline structure which leads to well-defined interface with 2D semiconductors and a low density of insulator defects. However, the most widely used 2D insulator is hexagonal boron nitride (hBN) which has a narrow bandgap (6eV) and a small dielectric constant (less than 5). This makes it difficult to maintain low gate leakage currents for hBN with sub-1nm EOT. Thus, alternative 2D insulators have to be urgently identified and characterized. Among these materials are mica, which outperforms hBN in terms of dielectric properties, and 2D oxide nanosheets. However, considerable processing advances are required to result in the demonstration of real devices.Finally, another interesting option would be the use of ionic crystals, such as epitaxial fluorides (e.g. CaF2, BaF2, and LaF3). Similar to 2D insulators, fluorides ideally contain a small number of defects and form well-defined interfaces with 2D semiconductors. Also, in contrast to hBN, they have good dielectric properties, e.g. a bandgap of 12.1 eV and a dielectric constant of 8.43 for CaF2. Recently, excellent performance of MoS2 FETs with 2nm thick epitaxial CaF2 (0.9nm EOT) has been achieved, which is currently impossible with any other insulator discussed above. Thus, further research on these insulators appears a very promising way for the development of scalable 2D FETs.In summary, the question about the most promising insulators for 2D FETs is still open. However, already now it is clear that successful integration of amorphous oxides into these devices appears problematic. Thus, it can be concluded that high-quality 2D FETs require crystalline insulators. These can be either layered 2D or ionic crystals with chemically inert surfaces, which generally address the fundamental limitations of oxides. Further research on these materials should target those which have the best dielectric properties and can be synthesized using fully scalable methods.

Structural and electronic properties of two-dimensional freestanding BaTiO3/SrTiO3 heterostructures

The successful preparation of the freestanding perovskite materials down to the monolayer limit [Ji et al., Nature (London) 570, 87 (2019)] provided the opportunity to make the two-dimensional (2D) oxide and heterostructure, which could be significantly distinctive from the conventional oxide superlattices and other 2D van der Waals heterostructures. By stacking one unit-cell $\mathrm{BaTi}{\mathrm{O}}_{3}$ (BTO) and one unit-cell $\mathrm{SrTi}{\mathrm{O}}_{3}$ (STO) on top of each other, we constructed two isolated bilayers of the 2D heterostructure systems. From our density functional theory simulation, their ground states exhibit an in-plane ferroelectricity in both BTO layer and STO layer, while the antiferrodistortive mode of the STO layer is totally suppressed. These two systems show band gaps in the range of 2--2.5 eV (by using HSE06), which are smaller than their monolayer and bulk phases. The layer arrangement strongly influences their electronic properties. We reveal that they adopt the type-II electronic band alignment. The tensile biaxial strain can strongly promote the ferroelectricity and increase the band gaps of these systems. Our results will contribute to the further understanding of layered materials based on the transition metal oxide perovskites and developing relevant experimental devices.

Memristive Behavior Enabled by Amorphous-Crystalline 2D Oxide Heterostructure.

The emergence of memristive behavior in amorphous-crystalline 2D oxide heterostructures, which are synthesized by atomic layer deposition (ALD) of a few-nanometer amorphous Al2 O3 layers onto atomically thin single-crystalline ZnO nanosheets, is demonstrated. The conduction mechanism is identified based on classic oxygen vacancy conductive channels. ZnO nanosheets provide a 2D host for oxygen vacancies, while the amorphous Al2 O3 facilitates the generation and stabilization of the oxygen vacancies. The conduction mechanism in the high-resistance state follows Poole-Frenkel emission, and in the the low-resistance state is fitted by the Mott-Gurney law. From the slope of the fitting curve, the mobility in the low-resistance state is estimated to be ≈2400 cm2 V-1 s-1 , which is the highest value reported in semiconductor oxides. When annealed at high temperature to eliminate oxygen vacancies, Al is doped into the ZnO nanosheet, and the memristive behavior disappears, further confirming the oxygen vacancies as being responsible for the memristive behavior. The 2D heterointerface offers opportunities for new design of high-performance memristor devices.

X-ray synthesis of noble metal nanoparticles onto 2D and 3D graphene oxide supports

Gold (Au), Palladium (Pd), and Ruthenium (Ru) nanoparticles were synthesized onto 2D and 3D graphene oxide using X-ray induced synthesis. Absorbed doses of ~20 kGy produced Pd and Au nanoparticles of ~5 nm and ~17 nm in size, respectively. Higher absorbed doses such as 60 kGy generated Ru nanoparticles with an average size of ~3 nm. CT-scan imaging confirmed metal particle formation inside the 3D graphene oxide supports, an advantage of X-ray induced synthesis over conventional approaches. The catalytic activity of Ru/GO monoliths, the smallest nanoparticles produced on monoliths, was tested through the olefination of alkyl acrylates. Results showed the high catalytic activity of the heterogeneous Ru catalysts structures similar to the homogeneous catalysis reported in the literature. Overall, this work demonstrates that X-ray assisted synthesis is a method that allows for nanoparticle formation at mild conditions of room temperature and pressure, in the absence of harsh chemicals in aqueous media suitable to fabricate catalysts in 2D and 3D carbon supports.

Metal Oxide Nanosheets as 2D Building Blocks for the Design of Novel Materials

Research into 2‐dimensional materials has soared during the last couple of years. Next to van der Waals type 2D materials such as graphene and h‐BN, less well‐known oxidic 2D equivalents also exist. Most 2D oxide nanosheets are derived from layered metal oxide phases, although few 2D oxide phases can be also made by bottom‐up solution syntheses. Owing to the strong electrostatic interactions within layered metal oxide crystals, a chemical process is usually needed to delaminate them into their 2D constituents. This Review article provides an overview of the synthesis of oxide nanosheets, and methods to assemble them into nanocomposites, mono‐ or multilayer films. In particular, the use of Langmuir–Blodgett methods to form monolayer films over large surface areas, and the emerging use of ink jet printing to form patterned functional films is emphasized. The utilization of nanosheets in various areas of technology, for example, electronics, energy storage and tribology, is illustrated, with special focus on their use as seed layers for epitaxial growth of thin films, and as electrochemically active electrodes for supercapacitors and Li ion batteries.

Two-Dimensional Amorphous SnOx from Liquid Metal: Mass Production, Phase Transfer, and Electrocatalytic CO2 Reduction toward Formic Acid.

Liquid metal forms a thin layer of oxide skin via exposure to oxygen and this layer could be exfoliated by mechanical delamination or gas-injection/solvent-dispersion. Although the room-temperature fabrication of two-dimensional (2D) oxide through gas-injection and water-dispersion has been successfully demonstrated, a synthetic protocol in nonaqueous solvent at elevated temperature still remains as a challenge. Herein we report the mass-production of amorphous 2D SnOx nanoflakes with Bi decoration from liquid Sn-Bi alloy and selected nonaqueous solvents. The functional groups of the solvents play a key role in determining the final morphology of the product and the hydroxyl-rich solvents exhibit the best control toward 2D SnOx. The different solvent-oxide interaction that facilitates this phase-transfer process is further discussed on the basis of DFT calculation. Finally, the as-obtained 2D SnOx is evaluated in electrocatalytic CO2 reduction with high faradaic efficiency (>90%) of formic acid and stable performance over 10 h.

Ferroelectric Behavior in Exfoliated 2D Aurivillius Oxide Flakes of Sub‐Unit Cell Thickness

AbstractFerroelectricity in ultrasonically exfoliated flakes of the layered Aurivillius oxide Bi5Ti3Fe0.5Co0.5O15 with a range of thicknesses is studied. These flakes have relatively large areas (linear dimensions many times the film thickness), thus classifying them as 2D materials. It is shown that ferroelectricity can exist in flakes with thicknesses of only 2.4 nm, which equals one‐half of the normal crystal unit cell. Piezoresponse force microscopy (PFM) demonstrates that these very thin flakes exhibit both piezoelectric effects and that the ferroelectric polarization can be reversibly switched. A new model is presented that permits the accurate modeling of the field‐on and field‐off PFM time domain and hysteresis loop responses from a ferroelectric during switching in the presence of charge injection, storage, and decay through a Schottky barrier at the electrode–oxide interface. The extracted values of spontaneous polarization, 0.04(±0.02) C m−2 and electrostrictive coefficient, 2(±0.1) × 10−2 m4 C−2 are in good agreement with other ferroelectric Aurivillius oxides. Coercive field scales with thickness, closely following the semi‐empirical scaling law expected for ferroelectric materials. This constitutes the first evidence for ferroelectricity in a 2D oxide material, and it offers the prospect of new devices that might use the useful properties associated with the switchable ferroelectric spontaneous polarization in a 2D materials format.

2-Mercaptobenzothiazole corrosion inhibitor deposited at ultra-low pressure on model copper surfaces

Adsorption of 2-mercaptobenzothiazole (2-MBT) at ultra-low pressure and room temperature on metallic and pre-oxidized Cu(111) surfaces and its thermal stability were investigated using X-ray photoelectron spectroscopy in order to better understand the interfacial corrosion inhibiting properties. 2-MBT is lying flat in the monolayer with two sulphur atoms bonded to Cu and decomposes partially yielding atomic sulphur when interacting with metallic copper prior to forming molecular multilayers. Decomposition is prevented by surface pre-oxidation with 2D oxide dissociation accelerating the 2-MBT initial adsorption kinetics. 2-MBT further decomposes and partially desorbs above 100 °C. A pre-adsorbed 2-MBT monolayer on metallic copper inhibits surface corrosion.

Adsorption and thermal stability of 2-mercaptobenzothiazole corrosion inhibitor on metallic and pre-oxidized Cu(1 1 1) model surfaces

2-mercaptobenzothiazole (2-MBT) is used for its corrosion inhibition properties. In this study, the adsorption of 2-MBT on metallic and pre-oxidized Cu(111) surfaces was investigated using Auger Electron Spectroscopy and Scanning Tunneling Microscopy. Growth and structure of molecular films adsorbed at ultra low pressure and room temperature on clean and pre-oxidized Cu(111) surfaces were characterized. On clean metallic Cu(111) surface, local triangular (7×7)R19.1° structures are formed at low exposures (3–4 L), which are assigned to the adsorption of atomic S resulting from partial decomposition of 2-MBT. At 10 L, a full non-ordered monolayer of 2-MBT is formed, and further exposure leads to the formation of a non-ordered multilayer. The thickness of the outermost 2-MBT layer is 1.3 Å, which suggests that the outermost molecules of the multilayer are lying flat. Oxidation of the copper surface prior to exposure to 2-MBT results in more compact and homogeneous molecular films. The initial 2D oxide is dissociated and replaced by 2-MBT. Thermal stability at different temperatures was studied on clean and pre-oxidized copper surfaces saturated with 2-MBT. A (7×7)R19.1° structure is observed in both cases for temperatures higher than 100°C, indicating the decomposition of 2-MBT and a copper surface covered with atomic S.

Tailoring magnetic order via atomically stacking 3d/5d electrons to achieve high-performance spintronic devices

The ability to tune magnetic orders, such as magnetic anisotropy and topological spin texture, is desired to achieve high-performance spintronic devices. A recent strategy has been to employ interfacial engineering techniques, such as the introduction of spin-correlated interfacial coupling, to tailor magnetic orders and achieve novel magnetic properties. We chose a unique polar–nonpolar LaMnO3/SrIrO3 superlattice because Mn (3d)/Ir (5d) oxides exhibit rich magnetic behaviors and strong spin–orbit coupling through the entanglement of their 3d and 5d electrons. Through magnetization and magnetotransport measurements, we found that the magnetic order is interface-dominated as the superlattice period is decreased. We were able to then effectively modify the magnetization, tilt of the ferromagnetic easy axis, and symmetry transition of the anisotropic magnetoresistance of the LaMnO3/SrIrO3 superlattice by introducing additional Mn (3d) and Ir (5d) interfaces. Further investigations using in-depth first-principles calculations and numerical simulations revealed that these magnetic behaviors could be understood by the 3d/5d electron correlation and Rashba spin–orbit coupling. The results reported here demonstrate a new route to synchronously engineer magnetic properties through the atomic stacking of different electrons, which would contribute to future applications in high-capacity storage devices and advanced computing.

Quasicrystals and their Approximants in 2D Ternary Oxides

2D oxide quasicrystals (OQCs) are recently discovered aperiodic, but well‐ordered oxide interfaces. In this topical review, an introduction to these new thin‐film systems is given. The concept of quasicrystals and their approximants is explained for and derived OQCs and related periodic structures in these 2D oxides. In situ microscopy unravels the high‐temperature formation process of OQCs on Pt(111). The dodecagonal structure is discussed regarding tiling statistics and tiling decoration based on the results of atomically resolved scanning tunneling microscopy and various diffraction techniques. In addition, angle‐resolved ultraviolet photoemission spectroscopy and X‐ray photoelectron spectroscopy results prove a metallic character of the 2D oxide.

Robust Ag/ZrO2/WS2/Pt Memristor for Neuromorphic Computing.

The development of the information age has made resistive random access memory (RRAM) a critical nanoscale memristor device (MD). However, due to the randomness of the area formed by the conductive filaments (CFs), the RRAM MD still suffers from a problem of insufficient reliability. In this study, the memristor of Ag/ZrO2/WS2/Pt structure is proposed for the first time, and a layer of two-dimensional (2D) WS2 nanosheets was inserted into the MD to form 2D material and oxide double-layer MD (2DOMD) to improve the reliability of single-layer devices. The results indicate that the electrochemical metallization memory cell exhibits a highly stable memristive switching and concentrated ON- and OFF-state voltage distribution, high speed (∼10 ns), and robust endurance (>109 cycles). This result is superior to MDs with a single-layer ZrO2 or WS2 film because two layers have different ion transport rates, thereby limiting the rupture/rejuvenation of CFs to the bilayer interface region, which can greatly reduce the randomness of CFs in MDs. Moreover, we used the handwritten recognition dataset (i.e., the Modified National Institute of Standards and Technology (MNIST) database) for neuromorphic simulations. Furthermore, biosynaptic functions and plasticity, including spike-timing-dependent plasticity and paired-pulse facilitation, have been successfully achieved. By incorporating 2D materials and oxides into a double-layer MD, the practical application of RRAM MD can be significantly enhanced to facilitate the development of artificial synapses for brain-enhanced computing systems in the future.

Perfect Monolayers of the BaTiO3‐Derived 2D Oxide Quasicrystals Investigated by Scanning Tunneling Microscopy and Noncontact Atomic Force Microscopy

The atomic structure of the BaTiO3‐derived 2D oxide quasicrystals (OQCs) is investigated using scanning tunneling microscopy (STM) and noncontact atomic force microscopy (nc‐AFM). It is demonstrated that these extraordinary films can easily be prepared as single‐phase monolayers on a Pt(111) support. From analyzing almost 20 000 atomic vertices, an extended statistical dataset of the OQC tiling is collected. It manifests that the OQC obeys the statistics of the Niizeki–Gähler tiling, which is a dodecagonal triangle–square–rhomb model system. The atomic structure shown by nc‐AFM is identical to the contrast obtained in STM images. The results are discussed with respect to the existing structural models.

Chern and Z2 topological insulating phases in perovskite-derived 4d and 5d oxide buckled honeycomb lattices

Based on density functional theory calculations including a Coulomb repulsion parameter U, we explore the topological properties of (LaXO3)2/(LaAlO3)4 (111) with X = 4d and 5d cations. The metastable ferromagnetic phases of LaTcO3 and LaPtO3 with preserved P321 symmetry emerge as Chern insulators (CI) with C = 2 and 1 and band gaps of 41 and 38 meV at the lateral lattice constant of LaAlO3, respectively. Berry curvatures, spin textures as well as edge states provide additional insight into the nature of the CI states. While for X = Tc the CI phase is further stabilized under tensile strain, for X = Pd and Pt a site disproportionation takes place when increasing the lateral lattice constant from aLAO to aLNO. The CI phase of X = Pt shows a strong dependence on the Hubbard U parameter with sign reversal for higher values associated with the change of band gap opening mechanism. Parallels to the previously studied (X2O3)1/(Al2O3)5 (0001) honeycomb corundum layers are discussed. Additionally, non-magnetic systems with X = Mo and W are identified as potential candidates for Z2 topological insulators at aLAO with band gaps of 26 and 60 meV, respectively. The computed edge states and Z2 invariants underpin the non-trivial topological properties.

Enhanced Ferromagnetism from Organic–Cerium Oxide Hybrid Ultrathin Nanosheets

Room-temperature ferromagnetism in two-dimensional (2D) oxide materials is an intriguing phenomenon for spintronic applications. Here, we report significantly enhanced room-temperature ferromagnetism observed from ultrathin cerium oxide nanosheets hybridized with organic surfactant molecules. The hybrid nanosheets were synthesized by ionic layer epitaxy over a large area at the water-air interface. The nanosheets exhibited a saturation magnetization of 0.149 emu/g as their thickness reduced to 0.67 nm. This value was 5 times higher than that for CeO2 thin films and more than 20 times higher than that for CeO2 nanoparticles. The magnetization was attributed to the high concentration (15.5%) of oxygen vacancies stabilized by surfactant hybridization as well as electron transfer between organic and oxide layers. This work brings an effective strategy of introducing strong ferromagnetism to functional oxide materials, which leads to a promising route toward exploring new physical properties in 2D hybrid nanomaterials.

Capture and emission mechanisms of defect states at interface between nitride semiconductor and gate oxides in GaN-based metal-oxide-semiconductor power transistors

A physical insight into the capture and emission behavior of interface/oxide states in a GaN-based metal-oxide-semiconductor (MOS) structure is of great importance to understanding the threshold voltage (VTH) instability in GaN power transistors. A time-dependent VTH shift in Ni/Al2O3/AlGaN/GaN MOS-HFETs (heterojunction field-effect transistors) and a distribution of Al2O3/III-nitride interface states (Dit) were successfully characterized by constant-capacitance deep level transient spectroscopy. It is found that in situ remote plasma pretreatments in plasma-enhanced atomic-layer-deposition could suppress Dit (EC-ET > 0.4 eV) down to below 1.3 × 1012 cm−2 eV−1. Under high applied gate bias (e.g., VG > 8 V), tunnel filling of oxide states in the Al2O3 dielectric comes into play, contributing to remarkable VTH instability in the MOS-HFETs. The tunnel distance between the 2D Electron Gas (2DEG) channel and oxide states ET,ox in the Al2O3 dielectric decreases from 3.75 to 0.82 nm as VG increases from 2 to 8 V. A further increase of VG to 11 V makes the Fermi level approach ET,ox (EC − ET ∼ 1.62 eV), which may enable direct filling. High electric field induced tunnel filling of gate oxide states could be an assignable cause for VTH instability in normally-OFF III-nitride MOS-HFETs.