National Institute Of Materials Physics - Romania

The reactions between [CuX(PPh3)](4) or [CuX(PPh3)(3)], X = Cl or Br, and N-benzoyl-N'-(4-methoxyphenyl)thio-urea (BTU-OMe), N-benzoyl-N'-(4-methylphenyl)thiourea (BTU-Me) in toluene gave new four-coordinated tetrahedral copper(I) complexes of two types: [CuX(BTU)(PPh3)(2)] (1, 2) and [CuX(BTU)(2)(PPh3)] (3,4) [BTU = N-benzoyl-N'-(4-methoxy/methyl phenyl)thiourea derivatives, X = Cl (a) and Br (b)]. These complexes were fully characterized by several analytical and spectroscopic (IR, UV/VIS, H-1, C-13 and P-31 NMR) techniques. The molecular structure of a representative complex, [Cu(BTU-OMe)(PPh3)(2)Cl] (3a), was determined by the single crystal X-ray diffraction method which reveals a distorted tetrahedral geometry where the Cu(I) ion is surrounded by one BTU ligand molecule, two PPh3 groups and one chloride anion. These eight heteroleptic complexes were found to emit in solid state with lifetimes in the 12-99 mu s range and with the highest quantum yield of 4.0% for 3b. The reaction between [CuBr(PPh3)](4) and N-benzoyl-N',N'-(di-n-butyl)thiourea (BTU-Bu-2) ligand gave the simple [CuBr(BTU-Bu-2)(3)] complex (5), when the PPh3 molecules were completely removed by the BTU derivative. The spectroscopic data indicated a distorted tetrahedral geometry produced by three BTU ligand molecules and one bromide anion. Complex 5 has the highest quantum yield (11%) with the lifetime of 29 mu s in solid-state.

To enhance the spectral response of solar cells, an experimental study on LaPO4:0.01Ce(3+)/xNd(3+) (x = 0, 2, 4 mol%) was carried out, where structural and morphological properties of the prepared samples were well characterized by the means of X-ray diffraction, Fourier transform infrared spectroscopy, and scanning electronic microscope. Additionally, the photoluminescence behavior of phosphors in ultraviolet-visible (UV-VIS) and Near-infrared (NIR) regions were investigated to confirm the energy transfer (ET) from Ce3+ to Nd3+. Moreover, the quantum efficiency of Ce3+/Nd3+-co-doped samples was estimated as high as similar to 172% and the possible ET process was described. Accordingly, the LaPO4:Ce3+/Nd3+ phosphors can convert the UV light (275 nm) into NIR photons (approx. 1059 nm) through the possible two-pathway energy transfer processes from Ce3+ sensitizer ions to Nd3+ activators. Obtained NIR down-conversion emissions are suitable for improving the conversion efficiency of c-Si solar cells.

Carbon-Titanium multilayer and composite thin films were obtained by Thermionic Vacuum Arc (TVA) method. The nanostructured films consisted by a carbon base layer and seven alternatively Titanium and Carbon layers were deposed on Silicon substrate. As well, to give C-Ti multilayer films with different percentages in Ti and C of layers, a thick Carbon base layer was deposed on Si substrate, and then seven Ti-C layers. In order to achieve the successively layers with C, and Ti different percentages, were adjusted the discharge parameters of C and Ti plasma sources to obtain the desired composition of layers. By changing of substrate temperature, and on the other hand the bias potential up to ???700V, different batches of samples were obtained. Characterization of structural properties of films was achieved by Grazing Incidence X-ray Diffraction (GIXRD) and Electron Microscopy technique (TEM). The measurements show that increase of the substrate temperature reveal the changes in TixCy lattice parameters. The tribological measurements were performed using a ball-on-disk system with normal forces of 0.5, 1, 2, 3N respectively and a Bruker Hystrion TI 980 TriboIndenter. Was found that the coefficient of friction depends on the synthesis temperature, bias voltage and also by the C content, Ti content and amount of TiC nanocrystallites. To characterize the electrical conductive properties, the electrical surface resistance versus temperature have been measured, and then the electrical conductivity is calculated. Using the Wiedeman-Frantz law was obtained the thermal conductivity.

Europium doped (0.1% and 1%) chlomborate BaO-B2O3-BaCl2 glass and glass-ceramic with embedded BaCl2 nanocrystals have been synthesised, investigated, and compared with the corresponding nanocrystalline powder. The structural analysis of the glass evidenced ionic bonds characteristic to the glass host structure and compositional changes during the melting. X-ray diffraction and transmission electron microscopy revealed the formation of orthorhombic BaCl2 nanocrystals of about tens on nm in size and a smaller amount of BaB2O4 nanocrystals. Structural analysis of the Eu2+-doped BaCl2 nanocrystals has shown a distortion of the crystalline cell assigned to the growth process, affected by defects and ionic impurities. Photoluminescence spectra of the glass-ceramic revealed Eu3+ and Eu2+ luminescent ion species, but only Eu2+ is incorporated within the BaCl2 nanocrystalline phase. Electron paramagnetic resonance measurements in X-band sustain the presence of Eu2+ ions. The EPR parameters (g values and hyperfine constants) resulting from the Q-band EPR spectra simulations recorded on glass-ceramic are similar to those in Eu2+-doped BaCl2 and confirmed the partial incorporation of Eu2+ ions within the BaCl2:Eu2+ nanocrystals in the glass-ceramics.

We investigated the optical and electrical properties of flexible single and bi-layer organic heterostructures prepared by vacuum evaporation with a p-type layer of arylenevinylene oligomers, based on carbazole, 3,3 ' bis(N hexylcarbazole)vinylbenzene = L13, or triphenylamine, 1,4 bis [4 (N,N' diphenylamino)phenylvinyl] benzene = L78, and an n-type layer of 5,10,15,20-tetra(4-pyrydil)21H,23H-porphyne = TPyP. Transparent conductor films of Al-doped ZnO (AZO) with high transparency, >90% for wavelengths > 400 nm, and low resistivity, between 6.9 x 10(-4) ohm center dot cm and 23 x 10(-4) ohm center dot cm, were deposited by pulsed laser deposition on flexible substrates of polyethylene terephthalate (PET). The properties of the heterostructures based on oligomers and zinc phthalocyanine (ZnPc) were compared, emphasizing the effect of the surface morphology. The measurements revealed a good absorption in the visible range of the PET/AZO/arylenevinylene oligomer/TPyP heterostructures and a typical injection contact behavior with linear (ZnPc, L78) or non-linear (L13) J-V characteristics in the dark, at voltages < 0.4 V. The heterostructure PET/AZO/L78/TPyP/Al showed a current density of ~1 mA/cm(2) at a voltage of 0.3 V. The correlation between the roughness exponent, evaluated from the height-height correlation function, grain shape, and electrical behavior was analyzed. Consequently, the oligomer based on triphenylamine could be a promising replacement of donor ZnPc in flexible electronic applications.

Nanoscale thermometers with high sensitivity are needed in domains which study quantum and classical effects at cryogenic temperatures. Here, we present a micrometer sized and nanometer thick chromium selenide cryogenic temperature sensor capable of measuring a large domain of cryogenic temperatures down to tenths of K. Hexagonal Cr-Se flakes were obtained by a simple physical vapor transport method and investigated using scanning electron microscopy, energy dispersive X-ray spectrometry and X-ray photoelectron spectroscopy measurements. The flakes were transferred onto Au contacts using a dry transfer method and resistivity measurements were performed in a temperature range from 7 K to 300 K. The collected data have been fitted by exponential functions. The excellent fit quality allowed for the further extrapolation of resistivity values down to tenths of K. It has been shown that the logarithmic sensitivity of the sensor computed over a large domain of cryogenic temperature is higher than the sensitivity of thermometers commonly used in industry and research. This study opens the way to produce Cr-Se sensors for classical and quantum cryogenic measurements.

In this work, new results concerning the potential of mixtures based on nitrogen doped titanium dioxide (TiO2:N) and carbon nanotubes (CNTs) as possible catalyst candidates for the rhodamine B (RhB) UV photodegradation are reported. The RhB photodegradation was evaluated by UV-VIS absorption spectroscopy using samples of TiO2:N and CNTs of the type of single-walled carbon nanotubes (SWNTs), double-wall carbon nanotubes (DWNTs), multi-wall carbon nanotubes (MWNTs), and single-walled carbon nanotubes functionalized with carboxyl groups (SWNT-COOH) having various concentrations of CNTs. The best photocatalytic performance was obtained for sample containing TiO2:N and 2.5 wt.% SWNTs-COOH, when approx. 85% of dye removal was achieved after 300 min. of UV irradiation. The reaction kinetics of RhB aqueous solutions containing TiO2:N/CNT mixtures followed a complex first-order kinetic model. The TiO2:N/CNTs catalyst induced higher photodegradation efficiency of RhB than TiO2:N due to the presence of CNTs, which act as adsorbent and dispersing agent and capture the photogenerated electrons of TiO2:N hindering the electron-hole recombination.

Herein, the properties of the organic heterostructures with triple-layer ZnO/Ag/ZnO as a replacement for ITO and mixed layer containing arylenevinylene oligomer (based on triphenylamine or carbazole) donor and nonfullerene (perylene diimide) acceptor mixed in the ratio 1:2 and the effect of a buffer layer of PEDOT-PSS intercalated between triple layer and mixed organic layer are discussed. The UV-vis transmission and photoluminescence (PL) properties are investigated in correlation with the surface topography and reveal a good match between the absorption and emission domain, which can favor the generation of the charge carriers. The heterostructure with the mixed layer based on triphenylamine oligomer shows the widest absorption domain, and the PL spectra of the heterostructures realized with either triphenylamine or carbazole oligomer show peaks corresponding to the radiative decay of the donor and acceptor. The I-V characteristics in the dark indicate a slightly nonlinear behavior and the current is affected by the charge carriers recombination on the defects present in the thick mixed layer deposited by matrix-assisted pulsed laser evaporation. The effect of the PEDOT-PSS buffer layer on the electrical properties of the organic heterostructure with ZnO/Ag/ZnO electrode is also investigated.

Amino-derivatized lignocomposite (ADL-composite) has been designed as an artificial lignin polymer (P1) of monolignol (coniferyl alcohol, CA) enhanced by aniline insertion (P2). The derivatized lignopolymeric (P2) layer covered the surface of a methacrylate particles (SC2/SC6) functionalized previously with amino phenolic crosslinker (p-phenylenediamine (p-Ph-2-NH2) or p-amino-2-hydroxybenzoic acid (p-NH2-SalA)). One-pot biocatalytic approach allowed to combine the preparation of the polymeric materials and also its attachment on the particles surface. Thus, the monolignol (CA) will be oxi-copolymerized together with aniline on the amino prefunctionalized support surface. The oxidation process was performed using H2O2 reagent and catalyzed by peroxidase enzyme (horseradish peroxidase, HRP). The biocatalytic process was evaluated in term of aromatic monomers (CA and aniline) conversion. The chemical structure and properties of the resulted ADL-composites were investigated using specific techniques (e.g. FTIR, TPD, TGA, static contact angle, elemental analysis, and gel permeation chromatography). Attachment of P1/P2 polymer on the particles improved the hydrophobicity and also the basicity of the composite surface. Lipase enzyme was immobilized on the ADL-composites for testing the applicability of ADL-composites for biocatalyst preparation. SEM analysis allowed to notice the modification of ADL-composites surface after enzyme immobilization. Immobilized lipase exhibited better activity compared with free lipase demonstrating the efficiency of ADL-composite as support for enzyme immobilization.