Olesya O. Kapitanova

Resistive Switching in Al/Graphene Oxide/Al Structure

We report resistive switching behaviors in an Al/graphene oxide/Al planar structure. Graphene oxide was synthesized by a modified Hummers method from graphite rods. The planar structures were fabricated on a Si/SiO2 substrate by spin-coating graphene oxide suspensions and patterning Al electrodes by photolithography. Both diode-like (rectifying) and resistor-like (nonrectifying) behaviors were observed in the device switching characteristics. Electrical characterization of the Al/graphene oxide interface using the induced current identified a potential barrier near the interface and its spatial modulation, caused by local changes of resistance at a bias voltage, which correlated well with the resistive switching of the whole structure. The mechanism of the observed local resistance changes near the electrode and the associated resistive switching of the entire structure is associated with the electrodiffusion of oxygen and the formation of sp2 graphene clusters in an sp3 insulating graphene oxide layer formed near the electrode by a pre-forming process.

Origin of long-range orientational pore ordering in anodic films on aluminium

Porous anodic aluminium oxide has a long history of practical application for corrosion protection and coloring. In the last few decades a lot of hi-tech applications of this material have been found owing to the discovery of anodization conditions leading to the formation of highly ordered porous structures with a narrow pore size distribution. Here we show that in-plane orientation of the porous system in anodic films on aluminium is fully determined by the intrinsic crystallographic orientation of the Al substrate. The anisotropy of aluminium oxidation rates on a scalloped metal–oxide interface leads to reorientation of Al spikes in certain directions, which builds up an in-plane orientational order on a macroscopic scale restricted by a crystallite size. This is a unique example of the inheritance of the substrate crystal structure by an amorphous film through a size difference of three orders of magnitude.

ZnO/MgO nanocomposites generated from alcoholic solutions

A process was proposed for the synthesis of ZnO/MgO nanocomposites from alcoholic solutions by means or the consecutive precipitation of coprecipitation of alcoholic solutions of zinc acetate and magnesium with an alkali solution followed by annealing in the range 400–500°C. X-ray powder diffraction showed crystalline ZnO and MgO phases in the resulting composite. Zinc oxide particle sizes in the composite with magnesium oxide were determined by transmission electron microscopy and from X-ray diffraction peak broadening. The zinc oxide nanoparticle size was weakly affected by the molar ratio of zinc to magnesium and the concentration of the precipitated component. The ZnO exciton peak in cathodoluminescence spectra for nanocomposites synthesized at low temperatures (400 and 500°C) shifted toward the UV. At ≥600°C or higher, Mg1 − xZnxO solid solution was generated, as evidenced by X-ray diffraction and cathodoluminescence data.

Formation of self-assembled nanoscale graphene/graphene oxide photomemristive heterojunctions using photocatalytic oxidation

Photocatalytic oxidation of graphene with ZnO nanoparticles was found to create self-assembled graphene oxide/graphene (G/GO) photosensitive heterostructures, which can be used as memristors. Oxygen groups released during photodecomposition of water molecules on the nanoparticles under ultraviolet light, oxidized graphene, locally forming the G/GO heterojunctions with ultra-high density. The G/GO nanostructures have non-linear current-voltage characteristics and switch the resistance in the dark and under white light, providing four resistive states at room temperature. Photocatalytic oxidation of graphene with ZnO nanoparticles is proposed as an effective method for creating two-dimensional memristors with a photoresistive switching for ultra-high capacity non-volatile memory.

Self-assembled MoS2/rGO nanocomposites with tunable UV-IR absorption

MoS2/reduced graphene oxide (rGO) nanocomposites were synthesized using an ultrasonic pretreatment with a single-stage hydrothermal and reduction process. Self-assembled MoS2 layers in the rGO matrix were obtained. The effect of quantum confinement in the structure, controlled by the degree of reduction of graphene oxide and the size of the 2D MoS2 nanocrystals, made it possible to obtain tunable optical absorption. MoS2/rGO layered nanocomposites exhibit a wide UV-IR absorption in the wavelength range from 280 nm to 973 nm, which is attractive for highly efficient multiband solar cells and advanced photonics.

Reduced graphene oxide in the construction of solid-state bromide-selective electrode

To improve the electrochemical performance of solid-state printed electrodes, reduced graphene oxide is used as an intermediate layer (mediator) between the surface layer of a current collector and the ionophore layer. A graphene oxide film was deposited onto the surface of printed electrodes by drop-casting, followed by reduction and electrochemical deposition. An ionic liquid 1,3-dihexadecylimidazolium bromide served as ionophore. The effect of reduced graphene oxide on the characteristics of the ion-selective electrode is studied, and it is shown that the sensors electrochemically modified with reduced graphene oxide have the best performance. These sensors exhibit a stable, well-reproducible response to bromide ions with the slope of the electrode function close to the Nernstian value (−60.7 ± 0.7 mV/dec) and a low detection limit of 3.6 × 10−6 M. The response time for all of the electrodes does not exceed 15 s even in dilute solutions.

Specifics of hydrothermal synthesis of oriented zinc oxide nanorods on metallic zinc substrates

Zinc oxide nanostructures are prepared hydrothermally in the presence of ethylenediamine (EDA). The morphology and photoluminescent properties of final products are studied as functions of synthesis temperature, synthesis time, and EDA concentration. A decrease in EDA concentration to 30% favors the formation of more perfect and more ordered structures. Blank experiments show that hydrothermal synthesis without organic reagents does not produce nanostructures. When samples are sheltered from convective flows in the cell, the rod growth direction is dictated by the grain orientation in the foil. When nanorods are formed under low supersaturations (in the absence of convective flows), oxygen nonstoichiometry arises in the nanorods and appears in photoluminescence spectra as increased peak intensities in the green spectral range.

Notable Reactivity of Acetonitrile Towards Li2O2/LiO2 Probed by NAP XPS During Li–O2 Battery Discharge

One of the key factors responsible for the poor cycleability of Li–O2 batteries is a formation of byproducts from irreversible reactions between electrolyte and discharge product Li2O2 and/or intermediate LiO2. Among many solvents that are used as electrolyte component for Li–O2 batteries, acetonitrile (MeCN) is believed to be relatively stable towards oxidation. Using near ambient pressure X-ray photoemission spectroscopy (NAP XPS), we characterized the reactivity of MeCN in the Li–O2 battery. For this purpose, we designed the model electrochemical cell assembled with solid electrolyte. We discharged it first in O2 and then exposed to MeCN vapor. Further, the discharge was carried out in O2 + MeCN mixture. We have demonstrated that being in contact with Li–O2 discharge products, MeCN oxidizes. This yields species that are weakly bonded to the surface and can be easily desorbed. That’s why they cannot be detected by the conventional XPS. Our results suggest that the respective chemical process most probably does not give rise to electrode passivation but can decrease considerably the Coulombic efficiency of the battery.

The effect of atmospheric doping on pressure-dependent Raman scattering in supported graphene

Atmospheric doping of supported graphene was investigated by Raman scattering under different pressures. Various Raman spectra parameters were found to depend on the pressure and the substrate material. The results are interpreted in terms of atmospheric adsorption leading to a change in graphene charge carrier density and the effect of the substrate on the electronic and phonon properties of graphene. It was found that adsorption of molecules from the atmosphere onto graphene doped with nitrogen (electron doping) compensates for the electron charge. Furthermore, the atmosphere-induced doping drastically decreases the spatial heterogeneity of charge carriers in graphene doped with nitrogen, while the opposite effect was observed for undoped samples. The results of this study should be taken into account for the development of sensors and nanoelectronic devices based on graphene.

Optical Properties of ZnO/MgO Nanocrystal Structures

The optical properties of ZnO/MgO nanocrystal structures were investigated with high spatial resolution. The green luminescence from as‐grown ZnO nanocrystals (tetrapods) is reduced after annealing the ZnO nanocrystals covered by MgO nanoparticles. Spatially‐resolved TLD and CL combined measurements showed that the depletion of ZnO nanocrystals by electrons leads to suppression of the green luminescence.