National Institute Of Materials Physics - Romania

The frequency and temperature dependence of dielectric properties of CH3NH3PbI3 (MAPI) crystals have been studied and analyzed in connection with temperature-dependent structural studies. The obtained results bring arguments for the existence of ferroelectricity and aim to complete the current knowledge on the thermally activated conduction mechanisms, in dark equilibrium and in the presence of a small external a.c. electric field. The study correlates the frequency-dispersive dielectric spectra with the conduction mechanisms and their relaxation processes, as well as with the different transport regimes indicated by the Nyquist plots. The different energy barriers revealed by the impedance spectroscopy highlight the dominant transport mechanisms in different frequency and temperature ranges, being associated with the bulk of the grains, their boundaries, and/or the electrodes' interfaces.

Ge2Sb2Te5 (GST-225) is a chalcogenide material with applications in nonvolatile memories. However, chalcogenide material properties are dependent on the deposition technique. GST-225 thin films were prepared using three deposition methods: magnetron sputtering (MS), pulsed laser deposition (PLD) and a deposition technique that combines MS and PLD, namely MSPLD. In the MSPLD technique, the same bulk target is used for sputtering but also for PLD at the same time. The structural and optical properties of the as-deposited and annealed thin films were characterized by Rutherford backscattering spectrometry, X-ray reflectometry, X-ray diffraction, Raman spectroscopy and spectroscopic ellipsometry. MS has the advantage of easily leading to fully amorphous films and to a single crystalline phase after annealing. MS also produces the highest optical contrast between the as-deposited and annealed films. PLD leads to the best stoichiometric transfer, whereas the annealed MSPLD films have the highest mass density. All the as-deposited films obtained with the three methods have a similar optical bandgap of approximately 0.7 eV, which decreases after annealing, mostly in the case of the MS sample. This study reveals that the properties of GST-225 are significantly influenced by the deposition technique, and the proper method should be selected when targeting a specific application. In particular, for electrical and optical phase change memories, MS is the best suited deposition method.

Cation-substituted hydroxyapatite (HA), standalone or as a composite (blended with polymers or metals), is currently regarded as a noteworthy candidate material for bone repair/regeneration either in the form of powders, porous scaffolds or coatings for endo-osseous dental and orthopaedic implants. As a response to the numerous contradictions reported in literature, this work presents, in one study, the physico-chemical properties and the cytocompatibility response of single cation-doped (Ce, Mg, Sr or Zn) HA nanopowders in a wide concentration range (0.5-5 at.%). The modification of composition, morphology, and structure was multiparametrically monitored via energy dispersive X-ray, X-ray photoelectron, Fourier-transform infrared and micro-Raman spectroscopy methods, as well as by transmission electron microscopy and X-ray diffraction. From a compositional point of view, Ce and Sr were well-incorporated in HA, while slight and pronounced deviations were observed for Mg and Zn, respectively. The change of the lattice parameters, crystallite size, and substituting cation occupation factors either in the Ca(I) or Ca(II) sites were further determined. Sr produced the most important HA structural changes. The in vitro biological performance was evaluated by the (i) determination of leached therapeutic cations (by inductively coupled plasma mass spectrometry) and (ii) assessment of cell behaviour by both conventional assays (e.g., proliferation-3-(4,5-dimethyl thiazol-2-yl) 5-(3-carboxymethoxyphenyl)-2-(4-sulfophenyl)-2H-tetrazolium assay; cytotoxicity-lactate dehydrogenase release assay) and, for the first time, real-time cell analysis (RTCA). Three cell lines were employed: fibroblast, osteoblast, and endothelial. When monophasic, the substituted HA supported the cells' viability and proliferation without signs of toxicity. The RTCA results indicate the excellent adherence of cells. The study strived to offer a perspective on the behaviour of Ce-, Mg-, Sr-, or Zn-substituted HAs and to deliver a well-encompassing viewpoint on their effects. This can be highly important for the future development of such bioceramics, paving the road toward the identification of candidates with highly promising therapeutic effects.

Composites of magnetite (Fe3O4) nanoparticles dispersed in a polydimethylsiloxane (PDMS) matrix were prepared by a molding process. Two types of samples were obtained by free polymerization with randomly dispersed particles and by polymerization in an applied magnetic field. The magnetite nanoparticles were obtained from magnetic micrograins of acicular goethite (alpha-FeOOH) and spherical hematite (alpha-Fe2O3), as demonstrated by XRD measurements. The evaluation of morphological and compositional properties of the PDMS:Fe3O4 composites, performed by SEM and EDX, showed that the magnetic particles were uniformly distributed in the polymer matrix. Addition of magnetic dispersions promotes an increase of thermal conductivity compared with pristine PDMS, while further orienting the powders in a magnetic field during the polymerization process induces a decrease of the thermal conductivity compared with the un-oriented samples. The shape of the magnetic dispersions is an important factor, acicular dispersions providing a higher value for thermal conductivity compared with classic commercial powders with almost spherical shapes.

The lack of order in amorphous chalcogenides offers them novel properties but also adds increased challenges in the discovery and design of advanced functional materials. The amorphous compositions in the Si-Ge-Te system are of interest for many applications such as optical data storage, optical sensors and Ovonic threshold switches. But an extended exploration of this system is still missing. In this study, magnetron co-sputtering is used for the combinatorial synthesis of thin film libraries, outside the glass formation domain. Compositional, structural and optical properties are investigated and discussed in the framework of topological constraint theory. The materials in the library are classified as stressed-rigid amorphous networks. The bandgap is heavily influenced by the Te content while the near-IR refractive index dependence on Ge concentration shows a minimum, which could be exploited in applications. A transition from a disordered to a more ordered amorphous network at 60 at% Te, is observed. The thermal stability study shows that the formed crystalline phases are dictated by the concentration of Ge and Te. New amorphous compositions in the Si-Ge-Te system were found and their properties explored, thus enabling an informed and rapid material selection and design for applications.

The structural role of V in 28Li(2)O-72SiO(2) (in mol%) lithium silicate glass doped with 0.5 mol% V2O5 was assessed using Si-29 and V-51 Nuclear Magnetic Resonance (NMR), Fourier-transform infrared (FTIR), and X-ray photoelectron (XPS) spectroscopy techniques. Despite the low amount of V2O5 used, the structural information obtained or deduced from the statistical analysis of the NMR data could explain the evolution of glass properties after V2O5 addition. The XPS results indicated that all vanadium exists in 5+ oxidation state. Both the Si-29 NMR and FTIR data point toward an increase in the polymerization of the silicate network, caused by the V2O5 acting as network former, capable to form various QVn tetrahedral units (for n = 0, 1, and 2) in the glasses. These QVn units, which are similar to phosphate units, scavenge the Li+ ions and cause the silicate network to polymerize. However, in an overall balance, the entire glass network is depolymerized due to the additional nonbridging oxygens contributed by the vanadium polyhedra. The addition of vanadium causes the network to expand and increases the ionic conductivity.

This Special Issue was devoted to developments made in Physical Vapour Deposited (PVD) biomedical coatings for various healthcare applications. The scrutinized PVD methods were Radio-Frequency Magnetron Sputtering (RF-MS), Cathodic Arc Evaporation, Pulsed Electron Deposition and its variants, Pulsed Laser Deposition, and Matrix Assisted Pulsed Laser Evaporation (MAPLE), due to their great promise especially in the dentistry and orthopaedics. These methods have yet to gain traction for industrialization and large-scale application in biomedicine. A new generation of implant coatings can be made available by the (1) incorporation of organic moieties (e.g., proteins, peptides, enzymes) into thin films by innovative methods such as combinatorial MAPLE, (2) direct coupling of therapeutic agents with bioactive glasses or ceramics within substituted or composite layers via RF-MS, or (3) by innovation in high energy deposition methods such as arc evaporation or pulsed electron beam methods.

In this work, amorphous tin oxide thin films were deposited by non-reactive radio frequency magnetron sputtering. A ceramic SnO2 target was used, while different working pressures were employed. The target to substrate distance was fixed to 17 cm, and the substrate was not intentionally heated. The properties of SnO2 (thickness, refractive index dispersion, optical band gap, resistivity, free carriers concentration, carriers mobility, carriers majority type and their scattering time) have been inferred from spectroscopic ellipsometry, conventional UV-Vis spectroscopy and specific Hall electrical measurements. Thickness and refractive index are slightly dependent on the deposition conditions, while the optical band gap, free carriers concentration and their mobilities are changing from sample to sample. The evolution of the optical band gap and carriers concentration is correlated to the active defects concentration. Amorphous SnO2 films grown at 0.4 Pa have the lowest resistivity of 0.86 Omega cm, a carrier concentration of 1.05x10(18)cm(-3) Vs. The average optical transmittance in visible spectrum is 76%.

Structural and electrical properties of epitaxial Pb(Zr0.2Ti0.8)O-3 films grown by pulsed laser deposition from targets with different purities are investigated in this study. One target was produced in-house by using high purity precursor oxides (at least 99.99%), and the other target was a commercial product (99.9% purity). It was found that the out-of-plane lattice constant is about 0.15% larger and the a domains amount is lower for the film grown from the commercial target. The polarization value is slightly lower, the dielectric constant is larger, and the height of the potential barrier at the electrode interfaces is larger for the film deposited from the pure target. The differences are attributed to the accidental impurities, with a larger amount in the commercial target as revealed by composition analysis using inductive coupling plasma-mass spectrometry. The heterovalent impurities can act as donors or acceptors, modifying the electronic characteristics. Thus, mastering impurities is a prerequisite for obtaining reliable and reproducible properties and advancing towards all ferroelectric devices.

Thin AlN piezoelectric layers have been deposited on high resistivity Si and glass substrates by reactive RF magnetron sputtering, in order to manufacture one-port gigahertz operating surface acoustic wave (SAW)-type resonators to be used as temperature sensors. The growth morphology surface topography, crystallographic structure, and crystalline quality of the AlN layers have been analyzed. Advanced nanolithographic techniques have been used to manufacture structures having interdigitated transducers with fingers and finger interdigit spacing width in the range of 250-170 nm. High resonance frequency ensures the increase of the sensitivity, but also of its normalized value, the temperature coefficient of frequency (TCF). The resonance frequency shift versus temperature has been measured in the -267 degrees C-+150 degrees C temperature range, using a cryostat setup adapted for on wafer microwave measurements up to 50 GHz. The sensitivity and the TCF were determined in the 25 degrees C-150 degrees C temperature range.