Aluminum Oxide Layers as Possible Components for Layered Tunnel Barriers

We have studied transport properties of Nb/Al/AlOx/Nb tunnel junctions with ultrathin aluminum oxide layers formed by (i) thermal oxidation and (ii) plasma oxidation, before and after rapid thermal post-annealing of the completed structures at temperatures up to 550 deg C. Post-annealing at temperatures above 300 deg C results in a significant decrease of the tunneling conductance of thermally-grown barriers, while plasma-grown barriers start to change only at annealing temperatures above 450 deg C. Fitting the experimental I-V curves of the junctions using the results of the microscopic theory of direct tunneling shows that the annealing of thermally-grown oxides at temperatures above 300 deg C results in a substantial increase of their average tunnel barriers height, from ~1.8 eV to ~2.45 eV, versus the practically unchanged height of ~2.0 eV for plasma-grown layers. This difference, together with high endurance of annealed barriers under electric stress (breakdown field above 10 MV/cm) may enable all-AlOx and SiO2/AlOx layered "crested" barriers for advanced floating-gate memory applications.Comment: 7 pages, 6 figure

Nanoscale-SiC doping for enhancing Jc and Hc2 in the Superconducting MgB2

The effect of nanoscale-SiC doping of MgB2 was investigated using transport and magnetic measurements. It was found that there is a clear correlation between the critical temperature Tc, the resistivity r, the residual resistivity ratio, RRR = R(300K)/R(40K), the irreversibility field H* and the alloying state in the samples. SiC-doping introduced many nano-scale precipitates, provoking an increase of r(40K) from 1 mW-cm (RRR = 15) for the clean limit sample to 300 mW-cm (RRR = 1.75) for the SiC-doped sample, leading to significant enhancement of Hc2 and H* with only minor effect on Tc. EELS analysis revealed a number of nano-scale impurity phases: Mg2Si, MgO, MgB4, BOx, SixByOz, BC and unreacted SiC in the doped sample. TEM study showed an extensive domain structure of 2-4nm domains induced by SiC doping. The Jc for the 10% nano-SiC doped sample increased substantially at all fields and temperatures compared to the undoped samples, due to the strong increase in Hc2 and H* produced by SiC doping

Direct observation of nm-scale Mg- and B-oxide phases at grain boundaries in MgB2

Here we describe the results of an atomic resolution study of the structure and composition of both the interior of the grains, and the grain boundaries in polycrystalline MgB2. We find that there is no oxygen within the bulk of the grains but significant oxygen enrichment at the grain boundaries. The majority of grain boundaries contain BOx phases smaller than the coherence length, while others contain larger areas of MgO sandwiched between BOx layers. Such results naturally explain the differences in connectivity between the grains observed by other techniques

Direct synthesis and chemical vapor deposition of 2D carbide and nitride MXenes

Two-dimensional (2D) transition metal carbides and nitrides (MXenes) are a large family of materials actively studied for various applications, especially in the field of energy storage. MXenes are commonly synthesized by etching the layered ternary compounds, MAX phases. We demonstrate a direct synthetic route for scalable and atom-economic synthesis of MXenes, including phases that have not been synthesized from MAX phases, by the reactions of metals and metal halides with graphite, methane, or nitrogen. The direct synthesis enables chemical vapor deposition (CVD) growth of MXene carpets and complex spherulite-like morphologies that form through buckling and release of MXene carpet to expose fresh surface for further reaction. The directly synthesized MXenes showed excellent energy storage capacity for Li-ion intercalation.Comment: 9 pages, 4 figure

Control of crystal size tailors the electrochemical performance of alpha-V2O5 as a Mg2+ intercalation host

α-V2O5 has been extensively explored as a Mg2+ intercalation host with potential as a battery cathode, offering high theoretical capacities and potentials vs. Mg2+/Mg. However, large voltage hysteresis is observed with Mg insertion and extraction, introducing significant and unacceptable round-trip energy losses with cycling. Conventional interpretations suggest that bulk ion transport of Mg2+ within the cathode particles is the major source of this hysteresis. Herein, we demonstrate that nanosizing α-V2O5 gives a measurable reduction to voltage hysteresis on the first cycle that substantially raises energy efficiency, indicating that mechanical formatting of the α-V2O5 particles contributes to hysteresis. However, no measurable improvement in hysteresis is found in the nanosized α-V2O5 in latter cycles despite the much shorter diffusion lengths, suggesting that other factors aside from Mg transport, such as Mg transfer between the electrolyte and electrode, contribute to this hysteresis. This observation is in sharp contrast to the conventional interpretation of Mg electrochemistry. Therefore, this study uncovers critical fundamental underpinning limiting factors in Mg battery electrochemistry, and constitutes a pivotal step towards a high-voltage, high-capacity electrode material suitable for Mg batteries with high energy density

Enhanced charge storage of nanometric ζ-V₂O₅ in Mg electrolytes

V2O5 is of interest as a Mg intercalation electrode material for Mg batteries, both in its thermodynamically stable layered polymorph (α-V2O5) and in its metastable tunnel structure (ζ-V2O5). However, such oxide cathodes typically display poor Mg insertion/removal kinetics, with large voltage hysteresis. Herein, we report the synthesis and evaluation of nanosized (ca. 100 nm) ζ-V2O5 in Mg-ion cells, which displays significantly enhanced electrochemical kinetics compared to microsized ζ-V2O5. This effect results in a significant boost in stable discharge capacity (130 mA h g−1) compared to bulk ζ-V2O5 (70 mA h g−1), with reduced voltage hysteresis (1.0 V compared to 1.4 V). This study reveals significant advancements in the use of ζ-V2O5 for Mg-based energy storage and yields a better understanding of the kinetic limiting factors for reversible magnesiation reactions into such phases

Hybrid organic-inorganic two-dimensional metal carbide MXenes with amido- and imido-terminated surfaces

Two-dimensional (2D) transition-metal carbides and nitrides (MXenes) show impressive performance in applications, such as supercapacitors, batteries, electromagnetic interference shielding, or electrocatalysis. These materials combine the electronic and mechanical properties of 2D inorganic crystals with chemically modifiable surfaces, and surface-engineered MXenes represent an ideal platform for fundamental and applied studies of interfaces in 2D functional materials. A natural step in structural engineering of MXene compounds is the development and understanding of MXenes with various organic functional groups covalently bound to inorganic 2D sheets. Such hybrid structures have the potential to unite the tailorability of organic molecules with the unique electronic properties of inorganic 2D solids. Here, we introduce a new family of hybrid MXenes (h-MXenes) with amido- and imido-bonding between organic and inorganic parts. The description of h-MXene structure requires an intricate mix of concepts from the fields of coordination chemistry, self-assembled monolayers (SAMs) and surface science. The optical properties of h-MXenes reveal coherent coupling between the organic and inorganic components. h-MXenes also show superior stability against hydrolysis in aqueous solutions.Comment: 10 pages, 4 figure