National Institute Of Materials Physics - Romania

A series of liquid crystals with various lanthanide ions (Eu-III, Sm-III, and Tb-III) was designed and prepared starting from the corresponding lanthanide nitrates and N-alkylated 4-pyridone derivatives bearing mesogenic 3,4,5-tris(alkyloxy)-benzyl moieties (alkyl=hexyl, octyl, decyl, dodecyl, tetradecyl, or hexadecyl). These new lanthanidomesogens were investigated for their mesogenic properties by a combination of differential scanning calorimetry, polarizing optical microscopy, and temperature-dependent powder X-ray diffraction (XRD). Their thermal stability was assessed by thermogravimetric analysis. All of these complexes show enantiotropic liquid-crystalline behavior with lamellar (SmA) phases in the case of shorter-chain complexes (C-6 and C-8) or hexagonal columnar phases (Col(h)) for complexes with longer alkyl chains (C-12, C-14, and C-16), which were assigned on the basis of their characteristic textures and XRD studies. For complexes with an intermediate number of carbon atoms in the side chains (C-10), both a lamellar phase at lower temperatures and a Col(h) phase at higher temperatures were evidenced. In the solid state, all these complexes show characteristic emissions assigned to the corresponding lanthanide ion. In addition, the luminescence decay curves showed single-exponential decays with characteristic times in the millisecond range (0.75-0.90 ms for Eu-III, 0.045-0.060 ms for Sm-III, and 0.75-1.05 ms for Tb-III).

We investigate the effect of the nature of the substrate and the bottom interface on the out-of-plane polarization orientation of ultrathin (10-nm) lead zirconate titanate (PZT) thin films of (001) orientation by photoelectron spectroscopy of samples without surface contamination. The substrate nature is varied between insulator (strontium titanate, STO) and semiconductor (Nb-doped STO, STON) and finally to a metal with a work function lower than that of PZT (strontium ruthenate, SRO). Outward polarization is obtained for PZT/STON(001) and inward polarization is obtained for PZT/STO(001) and PZT/SRO(001). Explanations are given for all these typical cases, the main elements being charge accumulation for compensation of the depolarization field, self-doping of PZT films, and the interface electric field driving the orientation of the polarization of the ferroelectric films. We find p-type self-doping is correlated with the inward polarization, and the driving field is formed between a negatively charged region with negatively ionized acceptors near the interface with the substrate and the p-type degenerate region with holes accumulated inside, toward the surface. This mechanism may be reversed under the assumption of n-type self-doping, positively ionized donors near the interface, and accumulated electrons toward the surface in the case of an interface with a substrate with a higher work function, being in line with recent data (PZT/Pt or BaTiO3/SRO).

Co-doped CeO2 thin films were grown from a bulk target with starting composition Ce0.95Yb0.04Er0.01O2 by pulsed laser deposition (PLD) on a p(+)-n-n(+) single crystal silicon diode. The PLD laser fluence was varied between 1.7 J/cm(2) and 3.7 J/cm(2). The device with the film grown for a laser fluence of 2.3 J/cm(2) delivers the highest performance taking advantage of the up conversion (UC) effect provided by this film. Namely, the increase in the relative power conversion efficiency of the device is 12.1% and 39.2% for illumination under 1 and 2.1 sun, respectively, and its relative external quantum efficiency is 8.2% when illuminated with 980 nm light. The film grown for the optimum 2.3 J/cm(2) fluence shows good target-film composition transfer and a granular morphology with a low roughness. The UC mechanism consists of efficient energy transfer between spatially separated Yb3+ and Er3+ ions, i.e. the absorption of infrared light photons by the Yb3+ ions (F-2(7/2) -> F-2(5/2) transition) is followed by a two-step energy transfer process to neighboring Er3+ ions and by their characteristic luminescent emissions ((H-2(11/2), S-4(3/2)) -> I-4(15/2)) and (F-4(9/2) -> I-4(15/2)).

This work involves the synthesis and characterization of Cu2ZnSnS4 (CZTS) layers. The films were prepared on ITO/glass substrate by ecofriendly and simple single-step electrodeposition method followed by sulfurization and annealing at 500 degrees C under Argon flow. By using two different complexing agents, the electrodeposition process can give better results. Therefore, the effect of combining the trisodium citrate - TC to multiple cornplexing agents (cetyl trimethyl ammonium bromide - CTAB, ethylene diamine tetra acetic acid - EDTA, Boric Acid - BA, Glutamic Acid - GA and Tartaric Acid - TA) is investigated. The characterization of the absorber films was done by X-ray diffraction (XRD) analysis, Raman spectroscopy, Scanning Electron Microscopy and Diffuse Reflectivity. The combination of TC and CTAB is suggested to be the best pair of complexing agents within the combinations used in this work.

Non-ionising energy loss of radiation produces point defects and defect clusters in silicon, which result in a significant degradation of sensor performance. In this contribution results from TSC (Thermally Stimulated Current) defect spectroscopy for silicon pad diodes irradiated by electrons to fluences of a few 10(14) cm(-2) and energies between 3.5 and 27 MeV for isochronal annealing between 80 and 280 degrees C, are presented. A method based on SRH (Shockley-Read-Hall) statistics is introduced, which assumes that the ionisation energy of the defects in a cluster depends on the fraction of occupied traps. The difference of ionisation energy of an isolated point defect and a fully occupied cluster, Delta E-a is extracted from the TSC data. For the VOt (vacancy-oxygen interstitial) defect Delta E-a = 0 is found, which confirms that it is a point defect, and validates the method for point defects. For clusters made of deep acceptors the Delta E-a values for different defects are determined after annealing at 80 degrees C as a function of electron energy, and for the irradiation with 15 MeV electrons as a function of annealing temperature. For the irradiation with 3.5 MeV electrons the value Delta E-a = 0 is found, whereas for the electron energies of 6-27 MeV Delta E-a > 0. This agrees with the expected threshold of about 5 MeV for cluster formation by electrons. The Delta E-a values determined as a function of annealing temperature show that the annealing rate is different for different defects. A naive diffusion model is used to estimate the temperature dependencies of the diffusion of the defects in the clusters.

The demand of calcium phosphate bioceramics for biomedical applications is constantly increasing. Efficient and cost-effective production can be achieved using naturally derived materials. In this work, calcium phosphate powders, obtained from dolomitic marble and Mytilus galloprovincialis seashells by a previously reported and improved Rathje method were used to fabricate microporous pellets through cold isostatic pressing followed by sintering at 1200 degrees C. The interaction of the developed materials with MC3T3-E1 pre-osteoblasts was explored in terms of cell adhesion, morphology, viability, proliferation, and differentiation to evaluate their potential for bone regeneration. Results showed appropriate cell adhesion and high viability without distinguishable differences in the morphological features. Likewise, the pre-osteoblast proliferation overtime on both naturally derived calcium phosphate materials showed a statistically significant increase comparable to that of commercial hydroxyapatite, used as reference material. Furthermore, evaluation of the intracellular alkaline phosphatase activity and collagen synthesis and deposition, used as markers of the osteogenic ability of these bioceramics, revealed that all samples promoted pre-osteoblast differentiation. However, a seashell-derived ceramic demonstrated a higher efficacy in inducing cell differentiation, almost equivalent to that of the commercial hydroxyapatite. Therefore, data obtained demonstrate that this naturally sourced calcium-phosphate material holds promise for applications in bone tissue regeneration.

The thermal stress effect on the structure of phase change memory materials, namely single films and double stacked films of GeTe and SnSe, is evaluated. The crystallization temperatures of GeTe and SnSe single films are 138 degrees C and 292 degrees C, respectively. The films are amorphous before annealing and crystallize in rhombohedral and orthorhombic structures afterwards. Ge is tetrahedrally bonded and Se is bivalent after deposition. Both Ge and Se have an octahedral configuration after annealing. The double stacked structure is studied in the as-deposited state and after annealing at temperatures of 100, 210, and 350 degrees C. Pulsed laser deposition produces the crystallization of both as-deposited layers when stacked, mostly of SnSe, but also some crystalline GeTe is present. GeTe fully crystallizes after annealing at 210 degrees C, in the face-centred cubic structure. Annealing at 350 degrees C leads to the evaporation of a significant quantity of Se and to the formation of a cubic Ge0.75Sn0.25Te solid solution. Ge has an octahedral coordination, while Se is tetrahedrally bonded as a result of a combination of bivalent amorphous Se and octahedral Se from crystalline SnSe. The study shows that diffusion between layers at high annealing temperatures might suppress the memory property and determines the formation of irreversible solid solutions.

Four Ge-based organometallic (OM = C6H10 Ge2O7) polymers with similar chemical composition were used as additions for MgB2. MgB2 (OM) 0.0014 dense samples with a relative density higher than 97% were obtained by ex situ spark plasma sintering. The critical current density and the irreversibility magnetic field of the added samples are slightly improved at high magnetic fields by repagermanium (Alfa Aesar) addition when compared to the pristine reference sample. Addition of Ge-straight-chain polymer shows some improvement of the maximum volume pinning force, F-p (max). There is no significant Ge substitution in the crystal lattice of MgB2, while C substitutes for B. Pinning mechanism is mainly of a point pinning type, with the grain boundary pinning mechanism strengthening at lower temperatures and when additives are not used. A relatively high amount of carbon in the samples washes out the Ge effects on pinning-force-related parameters. The structure and morphology of the polymer additive play an important role in dispersion when mixing, impacting the quality of the superconducting properties. The nanosize dimension of the pristine MgB2 powder shows also some drawbacks in mixing and sintering.

The osteogenic ions Ca2+ P5+, Mg2+, and antimicrobial ion Ga3+ were homogenously dispersed into a 1.45 mu m thick phosphate glass coating by plasma assisted sputtering onto commercially pure grade titanium. The objective was to deliver therapeutic ions in orthopaedic/dental implants such as cementeless endoprostheses or dental screws. The hardness 4.7 GPa and elastic modulus 69.7 GPa, of the coating were comparable to plasma sprayed hydroxyapatite/dental enamel, whilst superseding femoral cortical bone. To investigate the manufacturing challenge of translation from a target to vapour condensed coating, structural/compositional properties of the target (P51MQ) were compared to the coating (P40PVD) and a melt-quenched equivalent (P40MQ). Following condensation from P51MQ to P40PVD, P2O5 content reduced from 48.9 to 40.5 mol%. This depoly-merisation and reduction in the P-O-P bridging oxygen content as determined by P-31 NMR, FTIR and Raman spectroscopy techniques was attributed to a decrease in the P2O5 network former and increases in alkali/alkali-earth cations. P40PVD appeared denser (3.47 vs. 2.70 g cm(-3)) and more polymerised than it's compositionally equivalent P40MQ, showing that structure/ mechanical properties were affected by manufacturing route.