National Institute Of Materials Physics - Romania

In the present work, stannite Cu2CoSnS4 (CCTS) films were elaborated using spray pyrolysis method on soda-lime glass, at different deposition temperatures (T-d = 250, 300, and 350 degrees C), followed by different chosen sulfurization temperatures (T-s = 450, 500, and 550 degrees C). X-ray diffraction (XRD) revealed the nearly single-phase formation of CCTS films at 300 degrees C deposition temperature. After sulfurization in argon flow, the XRD lines become narrower, the average crystallite size expanding above 70 nm. The Raman spectroscopy analysis confirmed the stannite structure formation, as well as the presence CoS2 secondary phases, which reduces at higher sulfurization temperature (550 degrees C). The energy dispersive spectroscopy results indicated atomic ratios of Cu/Co/Sn/S close to the ideal stoichiometric ratio 2:1:1:4. The room temperature photoluminescence emission is recorded with maximum in the 1.35-1.40 eV range. Thermoelectric properties are measured up to 130 degrees C, the films show poor power factor as a result of small positive Seebeck coefficients 10-45 Of K -1 and low electrical conductivity despite of having relatively high carrier concentration (similar to 10(20) cm(-3)).

Understanding the phonon anharmonicity and temperature-dependent behavior of phonons that affect the thermal transport properties in 2D materials is crucial for developing efficient thermoelectric and memristor devices. SnSe has attracted significant interest because of its potential applications for developing such novel devices. Here, orthorhombic SnSe nanoflakes with a thickness of less than 100 nm and oriented along the [100] crystal axis were obtained using physical vapor transport at atmospheric pressure. Polarization-resolved Raman spectroscopy of SnSe nanoflakes was performed at a temperature of 5 K. Temperature-dependent frequencies and linewidths of Raman modes in tin selenide were fitted according to the anharmonic phonon coupling theory. The results indicate that both two and three order processes are responsible for the phonon decay in tin selenide. The memristive property was confirmed by electrical measurements of SnSe devices. SnSe memristors have an operating current of 10-4 A, similar to other transition-metal dichalcogenide memristors, but are more energy efficient than memristors based on defect migration, with a threshold voltage of 3 V.

A CuCrFeTiV high entropy alloy was prepared and irradiated with swift heavy ions in order to check its adequacy for use as a thermal barrier in future nuclear fusion reactors. The alloy was prepared from the elemental powders by ball milling, followed by consolidation by spark plasma sintering at 1178 K and 65 MPa. The samples were then irradiated at room temperature with 300 keV Ar+ ions with fluences in the 3 x 1015 to 3 x 1018 Ar+/cm2 range to mimic neutron-induced damage accumulation during a duty cycle of a fusion reactor. Structural changes were investigated by X-ray diffraction, and scanning electron microscopy and scanning transmission electron microscopy, both coupled with X-ray energy dispersive spectroscopy. Surface irradiation damage was detected for high fluences (3 x 1018 Ar+/cm2) with formation of blisters of up to 1 mu m in diameter. Cross-sectional scanning transmission electron microscopy showed the presence of intergranular cavities only in the sample irradiated with 3 x 1018 Ar+/cm2, while all irradiation experiments produced intragranular nanometric-sized bubbles with increased density for higher Ar+ fluence. The Williamson-Hall method revealed a decrease in the average crystallite size and an increase in residual strain with increasing fluence, consistent with the formation of Ar+ bubbles at the irradiated surface.

Novel (1-x) SrFe12O19 - x BNT-BT0.08 (x = 0; 0.5; 0.8; 1) nanocomposites were explored in this study. The samples were produced by sol-gel method and compacted by conventional sintering. The composition, morphology, local structure, dielectric and magnetic properties were investigated by X-ray diffraction, Transmission Electron Microscopy, Impedance Analysis, Mossbauer spectroscopy, and SQUID magnetometry. The desired composition and the presence of the magnetoplumbite SrFe12O19 and perovskite BNT-BT structures were verified by X-ray diffraction. Irregular morphology and large size distributions are evidenced in the electron microscopy micrographs. The reported room temperature dielectric constants in this study are the highest values obtained in multiferroic composites at room temperature: giant dielectric constants (similar to 1.3 x 10(6)) were obtained, relative to 0.13 x 10(4) in BNT-BT. The hyperfine parameters allowed the identification of the Wyckoff positions of the Fe ions corresponding closely to the theoretical case. The hard magnetic character of the SrFe12O19 phase is evidenced from the magnetic measurements. For the first time in multifermic composites, superdielectric characteristics are evidenced at room temperature.

The paper aims to identify the CO2 interaction mechanism for chemical sensors based on Gd-doped SnO2, SnO2 and Gd2O3 powders deposited as thick sensitive layers. The low reactivity of CO2 conferred by the thermodynamic stability and chemical inertia can be offset by the presence of relative humidity. The sensitive powders were prepared by wet chemical co-precipitation method. The Gd concentration was varied from 1% to 20 at% in order to determine the limit for Gd integration as a doping ion prior to chemical segregation as a secondary phase. Analytical transmission electron microscopy points to a homogeneous Gd doping of the nanostructured SnO2 powders for low doping concentrations and the formation of a nanocomposite based on SnO2 as main phase and cubic Gd2O3 as secondary phase for the highly doped samples. The electrical resistance is either influenced by the density of oxygen vacancies, or is the result of compensation for two opposite behaviours into the SnO2- Gd2O3 nanocomposite structures. The CO2 exposure to humid atmosphere determines distinct behaviours cor-responding to SnO2 and Gd2O3 as constitutive elements. The associated CO2 interaction mechanism is based on simultaneous DC electrical resistance and Contact Potential Difference measurements, which allow decoupling the ionosorption from the dipolar processes, thus highlighting specific chemical interactions on the SnO2 and Gd2O3 surfaces.

Designing complex electrochemical artificial muscles aims towards novel devices which besides excellent actuation capabilities should also present the ability to self-sense the modification of environmental parameters. In order to improve efficiency, mimicking the structure of natural muscles, synthetic actuators should have a similar fibrillary morphology. The importance of using materials based on fiber building blocks in actuators aimed at soft robotics field was demonstrated in the present report by comparing a fibrillary artificial muscle with one based on a classical film structure. Nylon electrospun fiber meshes and films were covered in the same conditions with a thin polypyrrole (PPy) layer. The fibrillary electrospun web morphology mimics that of natural muscles and the structure performs a fast, ample bending movement in liquid electrolyte when switching an applied electric potential between -0.6 and +0.6 V. Using the same actuation conditions, no movement of a film based artificial muscle was observed. In order to check the sensing ability of both fibrillary and film like electroactive architectures, their response i.e. PPy reaction when potential cycles were applied in different concentrations of LiClO4 electrolyte were recorded. The obtained results suggest that the ion exchange of the fibrillary artificial muscle is more efficient due to its higher active surface and such devices could work also as dual device (sensor/artificial muscle).

Pure and Er-doped hematite (alpha-Fe2O3) nanorods were prepared by a two-step method involving hydrothermal synthesis and calcination of pure and Er-doped goethite (alpha-FeOOH) nanorods. Substitution of Fe3+ by Er3+ in the crystal structure of hematite caused morpho-structural changes such as expansion of the unit cell and gradual shortening and rounding of hematite nanorods towards formation of nanoellipsoids. These changes induced modification of magnetic and optical properties suggesting the possibility of a systematic control of physical properties via rare earth substitution. A decrease in the hyperfine magnetic field, coercive field and Morin transition temperature, as well as an increase of the magnetic susceptibility and a narrowing of the optical band gap were observed by substitution. Intimate mechanisms related to the formation of more and more defect-like hematite phases with decreased temperatures for the transition to the low temperature antiferromagnetic phase at increased doping level were evidenced via temperature dependent Mo center dot ssbauer spectroscopy.

Due to the currently worldwide petrochemical feedstock shortage, the ethylene synthesis from renewable non-oil sources becomes of high interest. The catalysts were prepared in two steps: (i) formation of spheres containing the carbon-coated Mn core by hydrothermal method, (ii) formation of the Si-Zr oxide shell by sol-gel method. The prepared catalysts were characterized by N2 physisorption, SEM-EDX, XRD, XPS, and NH3-TPD. The catalytic results have shown that Fe, Zn or Ni modified Mn core exhibited superior activity compared to the catalysts containing only Mn in the core. With 75% yield and 98% ethanol conversion at 350 degrees C and WHSV of 1.4 h-1, MnNi@SiZr was the best catalyst. These results are due to an increased number of acid sites compared to the other materials and an optimal ratio of weak/medium acid sites. Our findings suggest new lines for developing active and stable catalysts for ethylene synthesis from ethanol.

Embedding electronic and optoelectronic devices in common, daily use objects is a fast developing field of research. New architectures are needed for migrating from the classic wafer- based substrates. Novel types of flexible PMMA/Au/Alq(3)/LiF/Al structures were obtained starting from electrospun polymer fibers. Thus, using an electrospinning process poly (methyl metacrylate) (PMMA) nanofibers were fabricated. A thin Au layer deposition rendered the fiber array conductive, this being further employed as the anode. The next steps consisted of the thermal evaporation of tris(8-hydroxyquinolinato) aluminum (Alq(3)) and aluminum deposition as the cathode. The Au covered PMMA nanofiber layer had a similar behavior with an indium tin oxide film i.e. low sheet resistance 10.6 omega/sq and high transparency. The low electrode resistivities allow an electron drift mobility of about 10(-6) cm(2) V-1 s(-1) at a low applied field, similar to the counterpart structures based on thin films. Concerning the relaxation processes in these structures, the Cole-Cole plots exhibit a slightly deformed semicircle, indicating a more complex equivalent circuit for the processes between metal electrodes and the active layer. This equivalent circuit includes reactance equivalent processes at the anode, cathode, in the active layer and most probably originates from the roughness of the metallic electrodes.

Flexible composites containing BaTiO3 nanoparticles into Gelatin bio-polymer matrix were designed and investigated. Following the idea that the electric field concentration in corners/edges at the interfaces between dissimilar materials give rise to enhanced effective permittivity in composites, cuboid-like BaTiO3 nanoparticles have been employed as nanofillers into Gelatin matrix by using an inexpensive solution-based processing method. As predicted by finite element method simulations developed for cubic-like inclusions into a homogeneous polymer matrix, the experimental permittivity of xBT-(1-x)Gelatin composites increases when increasing the high-permittivity filler addition. For the composition x = 40 wt% (corresponding to 12 vol% BaTiO3 addition), permittivity reaches epsilon r -15.7 with respect to epsilon r -9.8 of pure Gelatine (measured at 105 Hz), while the average piezoelectric coefficient d33 as determined by piezoelectric force microscopy shows a remarkable increase up to 21 pm/V in composites with x = 40 wt%, in comparison to -7 pm/V in pure Gelatin. By using the experimentally determined material constants, the simulated piezoelectric voltage output vs. time has shown a similar increase (about a doubling of its amplitude) of the harvesting signal in the composite with x = 40 wt% BT, with respect to one of the polymer matrix, thus demonstrating the beneficial role of embedding BT nanoparticles into the biopolymer for increasing the mechanical harvesting response.