National Institute Of Materials Physics - Romania

Due to its physical and chemical properties, the n-type tungsten oxide (WO3) semiconductor is a suitable photoanode for water decomposition reaction. The responses of the photoelectrochemical PEC water-splitting properties as an effect of structural and optical changes of WO3 thin films, as well as the nature of electrolyte solutions, were studied in this work. The WO3 thins films have been obtained by pulsed laser deposition (PLD) on silicon (Si(001)) covered with platinum substrates using three different laser wavelengths. As the XRD (X-ray diffraction) and XTEM (cross-section transmission electron microscopy) analysis shows, the formation of highly crystalline monocline WO3 phase is formed for the film deposited at 1064 nm wavelength and poor crystalline phases with a large ordering anisotropy, characteristic of 2D structures for the films deposited at 355 nm and 193 nm wavelengths, respectively. The photogenerated current densities J(ph) depend on the laser wavelength, in both alkaline and acidic electrolyte. The maximum values of the photocurrent density have been obtained for the sample prepared with laser emitting at 355 nm. This behavior can be correlated with the coherent crystallized atomic ordering that appear for long distances (10-15 nm) in the (001) plane of the monoclinic WO3 phase structure films obtained at 355 nm laser wavelength. All the samples show poor current density in dark conditions and they are very stable in both acidic and alkaline solutions. The highest photocurrent density value is obtained in acidic solution for the WO3 thin film prepared by 355 nm laser (29 mA/cm(2) at 1.6 V vs. RHE (1.35 V vs. Ag/AgCl)).

In this study, polystyrene composites (PS-GO(f)) with variable concentration (0.5; 1; 2; 3; 4; and 5 wt%) of GO(f) were obtained through the in-situ polymerisation of the styrene in the presence of benzoyl peroxide and graphene oxide(GO) functionalized with 3-(methacryloyloxy)-propyltrimethoxysilane(gamma-MPTS). For determining the morphological and structural particularities of polymeric composites transmission electron microscopy (TEM) measurements were performed. The influence of functionalized GO on thermal and combustion properties of polystyrene (PS)-based composite materials was determined through several methods: Thermogravimetry (TGA); derived thermogravimetry (DTG); microscale combustion calorimetry analysis (MCC); and chemical kinetic studies through TGA and MCC determinations at similar heating rates.

Green chemistry principles were used to phytosynthesis of three types of silver nanoparticles (AgNPs) from aqueous extracts of: nettle (Urtica dioica) leaves, black grapes (Vitis vinifera fruits), and their mixture. The combination of these extracts proved to be the most potent bioreductant for Ag+, as compared to each extract alone. UV-Vis absorption and FT-IR spectroscopy proved the formation of silver nanoparticles. Total polyphenols' quantification of vegetal extracts and "green" AgNPs was carried out by Folin-Ciocalteu analysis. Structural (XRD) analysis revealed crystalline nature of bio-developed AgNPs. Morphological studies (AFM) showed spherical shape and the nano-scale dimensions of the obtained metallic nanoparticles. Physical stability of "green" developed nanoparticles was estimated by zeta potential measurements, and their biological activity was checked by evaluating the antimicrobial and the antioxidant potency. AgNPs phyto-generated from a combination of two extracts (nettle and grapes) proved to be the most bio-active, combining in a synergistic manner, the properties of nettle and grapes. These nanoparticles exhibited high antioxidant activity (AA = 89.4%) evaluated through chemiluminescence method, and strong antibacterial effect (showing an inhibition zone diameter of 20 mm) against Escherichia coli.

This paper presents the study of the development of complex organic materials deposited by the Langmuir Blodgett technique. We have synthetized Langmuir Blodgett multilayers for the recognition of toxic chemicals in the air and / or ultraviolet radiation. The sensitive materials are based on multilayers of stearic acid metal salts combined with nanocarbon and metalloporphyrin structures. We prepared and obtained by the Langmuir Blodgett method films with nano-metric thicknesses combined in different concentrations of metal salts of fatty acids, Nano carbon structures and metalloporphyrins. Further we have characterized and tested the materials obtained for the sensitivity and selectivity of multilayers under the influence of various toxic gases and / or ultraviolet radiation obtaining high results in the field of sensors.

Stimulated Raman scattering (SRS) is studied in polycrystalline CdS/TiO2 mixtures based on laser power and temperature dependences in Raman investigation. Our Raman analysis reveals several features of nonlinear behavior, such as nonlinear laser power dependencies or high enhancement of Raman lines at a low temperature due to the intrinsic nonlinear nature of CdS, a high light scattering inside the matter, and a trap-based diffusive medium in a grain-boundary system. In particular, building up experimental evidence of conductivity at various temperatures, it is shown that the samples exhibit thermally activated conductivity due to potential local barriers revealed by a considerable fraction of the grain-boundaries in a diffusive medium. Taking into account the defect-based conductivity, a double Poole-Frenkel barrier is established within the grain-boundaries of CdS/TiO2 mixtures, and their barrier energies are investigated considering the temperature-dependent dark current of the grain-boundary model. We thus demonstrate that diffusive medium-based defects in a grain-boundary model makes CdS/TiO2 mixtures behave efficiently in nonlinear processes such as SRS. These features are of particular interest for optical communication technology, and the fundamental application of the SRS effect is semiconductor optical amplifiers.

In this paper we report a set of experiments at the wafer level regarding field-effect transistors with a graphene monolayer channel transferred on the ferroelectric HfO2/Ge-HfO2/HfO(2)three-layer structure. This kind of transistor has a switching ratio of 10(3)between on and off states due to the bandgap in graphene induced by the ferroelectric structure. Both top and back gates effectively control the carriers' charge flow in graphene. The transistor acts as a three-terminal memristor, termed a memtransistor, with applications in neuromorphic computation.

The matrix-assisted pulsed laser evaporation (MAPLE) technique was used for depositing thin films based on a recently developed conjugated polymer, poly[2,5-(2-octyldodecyl)-3,6-diketopyrrolopyrrole-alt-5,5-(2,5-di(thien-2-yl)thieno [3,2-b]thiophene)] (DPP-DTT) and fullerene C60 blends. The targets used in the MAPLE process were obtained by freezing chloroform solutions with different DPP-DTT:C60 weight ratios, with the MAPLE deposition being carried at a low laser fluence, varying the number of laser pulses. The structural, morphological, optical, and electrical properties of the DPP-DTT:C60 blend layers deposited by MAPLE were investigated in order to emphasize the influence of the DPP-DTT:C60 weight ratio and the number of laser pulses on these features. The preservation of the chemical structure of both DPP-DTT and C60 during the MAPLE deposition process is confirmed by the presence of their vibrational fingerprints in the FTIR spectra of the organic thin films. The UV-VIS and photoluminescence spectra of the obtained organic layers reveal the absorption bands attributed to DPP-DTT and the emission bands associated with C60, respectively. The morphology of the DPP-DTT:C60 blend films consists of aggregates and fibril-like structures. Regardless the DPP-DTT:C60 weight ratio and the number of laser pulses used during the MAPLE process, the current-voltage characteristics recorded, under illumination, of all structures developed on the MAPLE deposited layers evidenced a photovoltaic cell behavior. The results proved that the MAPLE emerges as a viable technique for depositing thin films based on conjugated polymers featured by a complex structure that can be further used to develop devices for applications in the solar cell area.

Nanocomposite thin films, sensitive to methane at the room temperature (25-30 degrees C), have been prepared, starting from SnSe2 powder and Zn(II)-5,10,15,20-tetrakis-(4-aminophenyl)- -porphyrin (ZnTAPP) powder, that were fully characterized by XRD, UV-VIS, FT-IR, Nuclear Magnetic Resonance (H-1-NMR and C-13-NMR), Atomic Force Microscopy (AFM), SEM and Electron Paramagnetic Resonance (EPR) techniques. Film deposition was made by drop casting from a suitable solvent for the two starting materials, after mixing them in an ultrasonic bath. The thickness of these films were estimated from SEM images, and found to be around 1.3 mu m. These thin films proved to be sensitive to a threshold methane (CH4) concentration as low as 1000 ppm, at a room temperature of about 25 degrees C, without the need for heating the sensing element. The nanocomposite material has a prompt and reproducible response to methane in the case of air, with 50% relative humidity (RH) as well. A comparison of the methane sensing performances of our new nanocomposite film with that of other recently reported methane sensitive materials is provided. It is suitable for signaling gas presence before reaching the critical lower explosion limit concentration of methane at 50,000 ppm.

ZnO nanostructures with intrinsic and extended defects were prepared by rapid decomposition of zinc-propio-nate and annealing at 400 degrees C-970 degrees C. The correlation between the structure/morphology, type of native defects (photoluminescence (PL), EPR) and ferromagnetism was investigated, together with ammonia adsorption capacity. All the samples show room temperature ferromagnetism (RTFM). Crystallite size increases while the unit cell volume, c-axis constant, microstrain and saturation magnetization relax with increasing temperature; morphology varies from aggregated nanoparticles to frameworks of well-welded crystals. 400 degrees C-800 degrees C annealed samples show a broad visible and/or a prominent violet-blue PL emission and, two narrow g = 2.0065 and g = 1.9632 EPR signals. 800 degrees C-970 degrees C annealed samples exhibit very intense green-yellow photoluminescence. The intrinsic defects in conjunction with a deformed lattice and/or pinned by grain-boundaries appear responsible for RTFM and Curie temperature exceeding 700 degrees C. Tuning the morphology, PL intensity and ferromagnetic signal by choice of annealing temperature can find applications in (gas) sensing, photonic/optoelectronic and spintronic devices.

An europium doped BaO-B2O3-BaCl2 chloroborate glass-ceramic containing a BaCl2 nanocrystalline phase was produced by melt-quenching followed by glass crystallization during annealing. Structural and morphological investigations using x-ray diffraction and scanning electron microscopy have shown fvBaCl(2) nanocrystals of about tens of nm size accompanied by a smaller amount of the BaB2O4 crystalline phase. Photoluminescence spectra have indicated the reduction of Eu3+ to Eu2+ during processing in air or a reducing atmosphere. The spectra analysis showed the presence of Eu3+ ions in the borate glass matrix, while the Eu2+ were incorporated in both the BaCl2 nanocrystals and glass matrix. Thermoluminescence properties were due to the recombination of F(Cl) centers and Eu2+ related hole centers produced by irradiation within the BaCl2 nanocrystals. The color impression of the samples and the photoluminescence quantum efficiency were influenced by the glass processing.