D. A. Kirilenko

The impact of ultra-low amounts of amino-modified MMT on dynamics and properties of densely cross-linked cyanate ester resins

Thermostable nanocomposites based on densely cross-linked cyanate ester resins (CER), derived from bisphenol E and doped by 0.01 to 5 wt. % amino-functionalized 2D montmorillonite (MMT) nanoparticles, were synthesized and characterized using Fourier transform infrared (FTIR), transmission electron microscopy (TEM), energy dispersive X-ray spectroscopy (EDXS), wide-angle X-ray diffraction (WAXD), dynamic mechanical analysis (DMA), differential scanning calorimetry (DSC), thermogravimetric analysis (TGA), far-infrared (Far-IR), and creep rate spectroscopy (CRS) techniques. It was revealed that ultra-low additives, e.g., 0.025 to 0.1 wt. %, of amino-MMT nanolayers covalently embedded into СER network exerted an anomalously large impact on its dynamics and properties resulting, in particular, in some suppression of dynamics, increasing the onset of glass transition temperature by 30° to 40° and twofold rise of modulus in temperature range from 20°C to 200°C. Contrarily, the effects became negligibly small or even negative at increased amino-MMT contents, especially at 2 and 5 wt. %. That could be explained by TEM/EDXS data displaying predominance of individual amino-MMT nanolayers and their thin (2 to 3 nanolayers) stacks over more thick tactoids (5 to 10 nanolayers) and the large amino-MMT aggregates (100 to 500 nm in thickness) reversing the composite structure produced with increasing of amino-MMT content within CER matrix. The revealed effect of ultra-low amino-MMT content testifies in favor of the idea about the extraordinarily enhanced long-range action of the ‘constrained dynamics’ effect in the case of densely cross-linked polymer networks.PACS82.35.Np Nanoparticles in polymers; 81.05.Qk Reinforced polymers and polymer-based composites; 81.07.Pr Organic-inorganic hybrid nanostructures

One-step synthesis of a suspended ultrathin graphene oxide film: application in transmission electron microscopy.

Ultrathin graphene films find their use as advantageous support for nano- and biomaterials investigations. Thin film causes a very slight deterioration to measured signals, thus providing more details of the objects structure at nanoscale. The ultimate thinness of graphene works in the best way for this purpose. However, obtaining suspended thin film of a large-area, which is convenient for applications, is often a relatively complicated and time-consuming task. Here we present a one-step 1-min technique for synthesis of an extremely thin (about 1-2 nm) continuous film suspended over cells of a conventional copper grid (50-400 μm mesh). This technique enables us to acquire a large-area film which is water-resistant, stable in organic solvents and can act as a support when studying nanoparticles or biomaterials. Moreover, the very mechanism of the film formation can be interesting from the point of view of other applications of ultrathin graphene oxide papers.

Observing visible-range photoluminescence in GaAs nanowires modified by laser irradiation

We study the structural and chemical transformations induced by focused laser beam in GaAs nanowires with an axial zinc-blende/wurtzite (ZB/WZ) heterostructure. The experiments are performed using a combination of transmission electron microscopy, energy-dispersive X-ray spectroscopy, Raman scattering, and photoluminescence spectroscopy. For both the components of heterostructure, laser irradiation under atmospheric air is found to produce a double surface layer which is composed of crystalline arsenic and of amorphous GaOx. The latter compound is responsible for the appearance of a peak at 1.76 eV in photoluminescence spectra of GaAs nanowires. Under an increased laser power density, due to sample heating, evaporation of the surface crystalline arsenic and formation of β-Ga2O3 nanocrystals proceed on the surface of the zinc-blende part of nanowire. The formed nanocrystals reveal a photoluminescence band in a visible range of 1.7–2.4 eV. At the same power density for wurtzite part of the nanowire, total a...

Insight into the performance of multi-color InGaN/GaN nanorod light emitting diodes

We report on the thorough investigation of light emitting diodes (LEDs) made of core-shell nanorods (NRs) with InGaN/GaN quantum wells (QWs) in the outer shell, which are grown on patterned substrates by metal-organic vapor phase epitaxy. The multi-bands emission of the LEDs covers nearly the whole visible region, including UV, blue, green, and orange ranges. The intensity of each emission is strongly dependent on the current density, however the LEDs demonstrate a rather low color saturation. Based on transmission electron microscopy data and comparing them with electroluminescence and photoluminescence spectra measured at different excitation powers and temperatures, we could identify the spatial origination of each of the emission bands. We show that their wavelengths and intensities are governed by different thicknesses of the QWs grown on different crystal facets of the NRs as well as corresponding polarization-induced electric fields. Also the InGaN incorporation strongly varies along the NRs, increasing at their tips and corners, which provides the red shift of emission. With increasing the current, the different QW regions are activated successively from the NR tips to the side-walls, resulting in different LED colors. Our findings can be used as a guideline to design effectively emitting multi-color NR-LEDs.

Unveiling structural, chemical and magnetic interfacial peculiarities in ε -Fe 2 O 3 /GaN (0001) epitaxial films

The metastable ε-Fe2O3 is known to be the most intriguing ferrimagnetic and multiferroic iron oxide phase exhibiting a bunch of exciting physical properties both below and above room temperature. The present paper unveils the structural and magnetic peculiarities of a few nm thick interface layer discovered in these films by a number of techniques. The polarized neutron reflectometry data suggests that the interface layer resembles GaFeO3 in composition and density and is magnetically softer than the rest of the ε-Fe2O3 film. While the in-depth density variation is in agreement with the transmission electron microscopy measurements, the layer-resolved magnetization profiles are qualitatively consistent with the unusual wasp-waist magnetization curves observed by superconducting quantum interference device magnetometry. Interestingly a noticeable Ga diffusion into the ε-Fe2O3 films has been detected by secondary ion mass spectroscopy providing a clue to the mechanisms guiding the nucleation of exotic metastable epsilon ferrite phase on GaN at high growth temperature and influencing the interfacial properties of the studied films.

Monodisperse core–shell particles composed of magnetite and dye-functionalized mesoporous silica

Hybrid particles with a core–shell structure have been obtained in the form of monodisperse spherical mesoporous silica particles filled with magnetite and covered with a mesoporous silica shell functionalized with a luminescent dye. The particles have a small root-mean-square size deviation (at most 10%), possess a specific surface area and specific pore volume of up to 250 m2/g and 0.15 cm3/g, respectively, and exhibit visible luminescence peaked at a wavelength of 530 nm. The particles can be used in diagnostics of cancerous diseases, serving simultaneously for therapeutic (magnetic hyperthermia and targeted drug delivery) and diagnostic (contrast agent for magnetic-resonance tomography and luminescent marker) purposes.

Nanoscale visualization of electronic properties of AlxGa1-xN/AlyGa1-yN multiple quantum-well heterostructure by spreading resistance microscopy

Cross-sectional spreading resistance microscopy has been used to investigate nanoscale variations in electronic properties of an undoped Al0.75Ga0.25N/Al0.95Ga0.05N multiple quantum well (MQW) heterostructure grown by plasma-assisted molecular beam epitaxy on an AlN/c-sapphire template, prepared by metalorganic vapor phase epitaxy. It is found that a current signal from the MQWs can be detected only at a negative sample bias. Moreover, its value changes periodically from one quantum well (QW) to another. Analysis of the current-voltage characteristics of the contacts of a tip with the structure layers showed that periodic contrast of MQWs is the result of fluctuations of the chemical composition of the QWs and the concentration of electrons accumulated in them. Mathematical simulations indicate that this modulation is associated with the periodic fluctuations of an Al-mole fraction in the barrier layers of the structure due to counter gradients of the intensity of Al and Ga molecular fluxes across the sur...

Nucleation of silica Stöber particles in the presence of methacryloxypropyltrimethoxysilane

The effect of 3-methacryloxypropyltrimethoxysilane (MPTMOS) on the nucleation of silica particles synthesized in a water−ethanol−ammonia−tetraethoxysilane (TEOS) mixture by the Stöber−Fink−Bohn method has been studied. It has been shown, using atomic force microscopy, that, as the content of MPTMOS in a TEOS + MPTMOS precursor mixture is increased from 0 to 12.5 mol %, the final silica particle size decreases from 470 to 10 nm, because the number of nucleation centers increases by several orders of magnitude. In contrast to TEOS, hydrolysis of MPTMOS yields a smaller amount of deprotonated orthosilicic acid monomers, the condensation of which is hindered by electrostatic repulsion. The polycondensation of electrically neutral products of MPTMOS hydrolysis gives rise to a larger number of nucleation centers in the reaction mixture.

New silver nanoparticles induce apoptosis-like process in E. coli and interfere with mammalian copper metabolism

Silver nanoparticles (SNPs) are new functional materials that are widely used in biomedical and industrial technologies. Two main features that make SNPs valuable are their strong antibacterial effects and low toxicity to eukaryotes. In this study, SNPs were synthesized using a modified method of reducing the metal ions to their atomic state followed by crystallization. SNPs were characterized by UV/vis spectroscopy, X-ray diffractometry, atomic force microscopy, and transmission electron microscopy (TEM). The SNPs were spherically shaped with an average linear dimension of 20 nm. In aqueous solution, the SNPs were beige-yellow in color, and they formed a black color in bacteria-rich growth media. The toxicity and bioavailability of the SNPs were tested using Escherichia coli cells and C57Bl/6 mice. Although the SNPs displayed bactericidal activity, an E. coli cell strain transformed with an expression plasmid carrying a human CTR1 ectodomain with three motives that bind Cu(II), Cu(I), and Ag(I) demonstrated increased resistance to treatment with SNPs. TEM showed that the SNPs were absorbed by the E. coli cell, and flow cytometry showed that the SNPs induced apoptosis-like death. In mice treated with SNPs (daily intraperitoneal injection of 10 μg SNPs/g body weight over 4 days), the ceruloplasmin (Cp) oxidase activity in the blood serum decreased. However, level of Cp gene expression, the relative contents of the Cp protein in the Golgi complex and in the serum did not change. Treatment with SNPs did not influence the activity of superoxide dismutase 1 in the liver and had no apparent toxic effects in mice. These findings expand the scope of application for the use of new SNPs. The data are discussed in a paradigm, in which the effects of SNPs are caused by the interference of silver ions with copper metabolism.

Site-Controlled Growth of GaN Nanorods with Inserted InGaN Quantum Wells on μ-Cone Patterned Sapphire Substrates by Plasma-Assisted MBE

We report on a new approach to fabricate regular arrays of GaN nanorods (NRs) with InGaN QWs by plasma-assisted molecular-beam epitaxy (PA MBE) on micro-cone patterned sapphire substrates (μ-CPSSs). A two-stage PA MBE fabrication process of GaN NRs has been developed, starting with a high temperature nucleation layer growth at metal-rich conditions to aggregate selectively GaN nucleus on c-oriented areas of the μ-CPSSs and followed by growth of 1-μm-thick GaN NRs at strongly nitrogen-rich conditions exactly on the cone tips. These results are explained by energetically favorable GaN growth on the (000-) oriented sapphire surface. Both micro-photoluminescence and micro-cathodoluminescence confirm the formation of regular array of optically and spectrally isolated NRs without usage of any nanolithography.